Let $k$ be a field, $G$ a group and $R$ a $k$-algebra (i.e. a ring $R$ with a homomorphism $i : k \rightarrow Z(R)$). The claim is that there is a natural bijection between the set of $k$-algebra homomorphisms $k[G] \rightarrow R$ and the set of group homomorphisms $G \rightarrow R^*$. I suppose this statement could be denoted
Hom$_{i[k]}(k[G], R) \approx$ Hom$(G,R^*)$
(as $k$-algebra homomorphisms are, I believe, simply those ring homomorphisms which are $i[k]-$linear). (Note also that $k$ itself is a $k$-algebra: as $Z(k) = k$, we can simply take $i$ to be the identity.)
Am I getting this right so far?
So given a $k$-algebra homomorphism $\phi : k[G] \rightarrow R$, I should be able to map it onto a group homomorphism $f : G \rightarrow R^*$, and back.
I would say we want to do something like "$f = \phi|_G$", as it seems clear that then $f[G] \subseteq R^*$.
First we define $\varphi: \text{Hom}_{i(k)}(k[G], R) \to \text{Hom}(G,R^*)$. Let $f:k[G] \to R$ be a $k$-algebra homomorphism. Define $\varphi(f)$ by $\varphi(f)(g) = f(g)$ for each $g \in G$.
I claim $\varphi(f)$ is a group homomorphism from $G$ to $R^*$. First note that, for any $g \in G$, $$\varphi(f)(g)\varphi(f)(g^{-1}) = f(g)f(g^{-1}) = f(gg^{-1}) = f(1) = 1.$$ Thus, for any $g \in G$, $\varphi(f)(g) \in R^*$. It follows quickly from the definition that $\varphi(f)$ is a group homomorphism.
To see that $\varphi$ is bijective, define $\psi:\text{Hom}(G,R^*) \to \text{Hom}_{i(k)}(k[G], R)$ as follows. Given $f:G \to R^*$ define $\psi(f)\left(\sum_{g \in G} c_g g\right) = \sum_{g \in G}i(c_g)f(g)$. The fact that $\psi(f)$ is a $k$-algebra homomorphism will follow from the fact that $f$ is a group homomorphism. You can also quickly check that $\varphi = \psi^{-1}$.