Let ${\rm Vec}_{\mathbb{R}}$ denote the category of finite dimensional vector spaces over the real numbers. Let ${\rm Hom}_k(V,W)$ denote the space of multilinear maps $\underbrace{V\times\dots\times V}_{k\ times} \to W$ and $V_k^1$ denote the space of multilinear maps $\underbrace{V\times\dots\times V}_{k\ times} \times V^* \to \mathbb{R}$.
I want to show that there is a natural isomorphism between $Hom_k(V,V)$ and $V_k^1$. I have reduced the problem to showing the existence of a natural isomorphism between $Hom_k(V,V^{**})$ and $V_k^1$. Intuitively it is clear to me that such an identification can be accomplished by currying, that this is a vector space isomorphism should be verifiable simply by checking the definitions, and that naturality should follow from (some variant of) the Yoneda Lemma. However, I am having some difficulty finding the endofunctors in $Vec_{\mathbb{R}}$ that would allow me to verify all of these claims.
Reduction: I know that, given a finite dimensional vector space $V$, there is a natural isomorphism with $V^{**}$. Using hom functors, it isn't that difficult to extend this to a natural isomorphism between $Hom_k(V,V)$ and $Hom_k(V,V^{**})$.
What I have tried: I have tried to find functors $$f_1: Vec_{\mathbb{R}} \to Vec_{\mathbb{R}}, V \mapsto Hom_k(V,V^{**})$$ and $$f_2: Vec_{\mathbb{R}} \to Vec_{\mathbb{R}}, V\mapsto V_k^1.$$ However, given vector space homomorphisms $T:V\to W$, it is unclear to me how to find vector space homomorphisms $Hom_k(V,V^{**}) \to Hom_k(W,W^{**})$ or $Hom_k(W,W^{**}) \to Hom_k(V,V^{**})$ which would give the morphism part of the functors. First I tried using a contravariant hom functor, i.e. pre-composition by T, $$T \mapsto f(T(\cdot),\dots,T(\cdot)),$$ but the problem with this is that it only maps $Hom_k(W,W^{**}) \to Hom_k(V,W^{**})$, but clearly I need a map $Hom_k(W,W^{**}) \to Hom_k(V,V^{**})$.
So then I tried restricting from $Vec_{\mathbb{R}}$ to the subcategory $\mathbb{V}$, defined to be the category whose objects are all $n$-dimensional vector spaces over $\mathbb{R}$ and whose morphisms consist only of invertible linear transformations, and then finding functors $$f_1: \mathbb{V} \to Vec_{\mathbb{R}}, \quad f_2: \mathbb{V} \to Vec_{\mathbb{R}},$$ with the same rules of assignment for the objects as before, namely $f_1: V \mapsto Hom(V,V^{**})$ and $f_2: V \mapsto V_k^1$. Then I tried the following rule of assignment for morphisms for $f_1$: $$T\mapsto T^{-1} f(T(\cdot),\dots,T(\cdot))$$ -- this does map $Hom_k(W,W^{**})\to Hom_k(V,V^{**})$ as desired, but it turns out this satisfies neither associativity nor functoriality. Now I am stuck. I haven't tried to find a rule of assignment for morphisms for $f_2$, but it seems like one would run into the analogous problems.
However, without two endofunctors $f_1$ and $f_2$, I can't show that there is a natural transformation between them which is also an isomorphism and which is a vector space isomorphism when applied to objects.
In terms of exponential objects, I think what I want to show is equivalent to: $$ V^{V^k} \cong \mathbb{R}^{V^k \otimes V^*} .$$ Then what I have reduced it to is showing $$ V^{V^k} \cong (\mathbb{R}^{V^*})^{V^k} \cong \mathbb{R}^{V^k \otimes V^*} .$$ Now the left isomorphism is essentially easy, since $V \cong V^{**}:=\mathbb{R}^{V^*}$, so what I need to show is the right isomorphism, which is the vector space version of the natural exponential object correspondence. So if I can prove that $(X^Y)^Z \cong X^{Y \times Z}$ in $Set$, then maybe the proof will carry over almost word for word for the corresponding version in $Vec_{\mathbb{R}}$. I still need to look into this line of approach more, although so far I have not succeeded yet in demonstrating the naturality of the isomorphism $(X^Y)^Z \cong X^{Y \times Z}$ in $Set$, so it might not be as easy as I am hoping.
EDIT: If I can show that $Vec_{\mathbb{R}}$ is Cartesian closed, then this should follow from Exercise 1(b), section 6.6., p.123, of Awodey's Category Theory. Although the exercise is only to prove that we have an isomorphism, $(A^B)^C \cong A^{B \times C}$, but does not include a proof of naturality.
Your "functors" aren't actually functors. I'll stick to standard notations because "$\operatorname{Hom}_k(V,V)$" is too easy to mistake for the space of $k$-linears maps $V \to V$ for some field $k$... I'll also let the base field $\mathbb{R}$ be implied throughout.
Let's do the simplest case, $k=1$. Then you have a bifunctor $$\operatorname{Hom} : \mathsf{Vec}^{\mathrm{op}} \times \mathsf{Vec} \to \mathsf{Vec}, \; (V,W) \mapsto \operatorname{Hom}(V,W)$$ It's not possible to compose that with the functor $\mathsf{Vec} \to \mathsf{Vec} \times \mathsf{Vec}$, simply because the (co)domains don't match... So the mapping $V \mapsto \operatorname{Hom}(V,V)$ doesn't yield a functor a priori. I can't see any reasonable way to make that into a functor. Your question is doomed from the start...
However you do have the bifunctor $\operatorname{Hom}$ as above. You also have another bifunctor, say $$\Phi : \mathsf{Vec}^{\mathrm{op}} \times \mathsf{Vec} \to \mathsf{Vec}, \; (V,W) \mapsto \operatorname{Hom}(V \otimes W^*, \mathbb{R}).$$
This is indeed a bifunctor; given $f : V' \to V$ and $g : W \to W'$, you get $\Phi(f,g) : \Phi(V,W) \to \Phi(V',W')$ given by $t \mapsto t \circ (f \otimes g^*)$ (where $g^* : \operatorname{Hom}(W', \mathbb{R}) \to \operatorname{Hom}(W,\mathbb{R})$ is precomposition by $g$).
These two functors are naturally isomorphic, when you restrict to finite-dimensional spaces. Indeed define a natural transformation $\eta : \operatorname{Hom} \to \Phi$ by: \begin{align} \eta_{(V,W)} : \operatorname{Hom}(V,W) & \to \operatorname{Hom}(V \otimes W^*, \mathbb{R}) \\ t & \mapsto (\eta(t) : v \otimes \psi \mapsto \psi(t(v))) \end{align}
It's not hard (but it's a bit tedious) to check that this is a natural transformation. Both spaces have the same dimension, namely $(\dim V) (\dim W)$. So to check that this is an isomorphism for all $(V,W) \in \mathsf{Vec}^\mathrm{op} \times \mathsf{Vec}$, it suffices to check that this is surjective.
For a fixed couple $(V,W)$, let $(w_1, \dots, w_n)$ be a basis of $W$ (recall that it's finite dimensional), and let $(w_1^*, \dots, w_n^*)$ be the dual basis of $W^*$. Suppose given some $\beta \in \operatorname{Hom}(V \otimes W^*, \mathbb{R})$. Then you can let $\alpha \in \operatorname{Hom}(V, W)$ be defined by $$\alpha(v) = \sum_{i=1}^n \beta(v \otimes w_i^*) \cdot w_i.$$
It is now a very tedious (but completely mechanical) check that $\eta_{(V,W)}(\alpha) = \beta$. The mapping is surjective between spaces of the same finite dimension, hence it's an isomorphism.
Finally, to get the general case, consider the functor $\bigotimes : \mathsf{Vec}^{\times k} \to \mathsf{Vec}$ given by $\bigotimes(V_1, \dots, V_k) = V_1 \otimes \dots \otimes V_k$, and compose it with the natural isomorphism $\eta$ to get a natural isomorphism $$\operatorname{Hom}(V_1 \otimes \dots \otimes V_k, W) \xrightarrow{\cong} \operatorname{Hom}(V_1 \otimes \dots \otimes V_k \otimes W^*, \mathbb{R}).$$
But again this is contravariant in the $V_i$ and covariant in $W$, so you can compose with $V \mapsto (V, \dots, V)$ because this is covariant in everything...