There several questions about linear transformations and its respective matrices in some basis, but I'm particularly interested in the explicit definition of this relation in the category $Vect$ (of vector spaces and linear transformations.) Of course, a inevitable question is if there is always an matrix (or tensor, perhaps) representation (representable Functor?) for every morphism in an arbitrary category. Sorry if it is a silly question, but I'm learning CT by myself and it is difficult for me to understand this relation in categorical terms.
What's the explicit categorical relation between a linear transformation and its matrix representation?
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Let $F$ be a field.
The category $\mathbf{Vect}_F$ of vector spaces over $F$ with linear transformations has a subcategory $\mathbf{FVect}_F$ of finite-dimentional vector spaces with linear transformation.
There's also a (small) category $\mathbf{Mat}_F$ whose objects are the natural numbers and morphisms are matrices with entries on $F$. Composition is matrix multiplication.
Now, each choice of an ordered basis for every vector space in $\mathbf{FVect}_F$ (or a full subcategory of it) gives rise to a full and faithful functor $\mathbf{FVect}_F\to\mathbf{Mat}_F$ which represents each linear transtformation by its matrix.
In particular, the fact that the functor is full and faithful means that if $V$ and $W$ are vector spaces of dimension $m$ and $n$, then $\operatorname{Hom}_{\mathbf{FVect}}(V,W)\cong \operatorname{Hom}_{\mathbf{Mat}}(m,n)$, which says that each linear transformation corresponds to exactly one matrix and vice versa.
This is, in fact, a pretty good concrete example to keep in mind of how a "full and faithful functor" behaves.
Alternatively -- especially if we have foundational quibbles over the idea of choosing a particular basis for each of the proper-class-many objects of $\mathbf{FVect}_F$ -- we could define a new cateory $\mathbf{FVectB}_F$ in which an object is a finite vector space together with an ordered basis for it. Then there is a single canonical full-and-faithful functor $\mathbf{FVectB}_F\to\mathbf{Mat}_F$. On the other hand, it feels a bit strange to introduce a distinction between the objects in $\mathbf{FVectB}$ that doesn't participate at all in deciding what the morphisms are and how they compose -- but seen at the categorical level that is really not that different from having multiple isomorphic objects in a category, which happens already for $\mathbf{FVect}$ itself.
Let $\Bbbk$ be a field and $\mathsf{Vec}_f$ the category of finite dimensional vector spaces over $\Bbbk$. Let also $\mathsf{Mat}$ be the category whose objects are natural number $n \ge 0$, morphism $n \to m$ are matrices $m \times n$ with entries in $\Bbbk$, and composition is matrix multiplication.
There is a functor $F : \mathsf{Mat} \to \mathsf{Vec}_f$ given by $F(n) = \Bbbk^n$ and $F(M)$ is the linear map represented by $M$ in the standard bases of $\Bbbk^m$ and $\Bbbk^n$.
Then this functor is full and faithful: the induced map $F : \hom_\mathsf{Mat}(m,n) \to \hom_{\mathsf{Vec}_f}(\Bbbk^m, \Bbbk^n)$ is a bijection (this is a standard fact about linear algebra). It's also essentially surjective: every finite dimensional vector space is isomorphic to $\Bbbk^n$ for some $n$. Therefore it's an equivalence of categories.
This is very similar to Henning Makholm's answer, but his is mixing up two issues: the existence of the equivalence of categories $F$, and the existence of a pseudo-inverse to an equivalence of categories using some kind of choice.