This question was already discussed here:
Why is Hom(V,W) the same thing as V∗⊗W?
But, I want to take a different approach in proving that
$$\phi:V^*\otimes W\to \text{Hom}(V,W)$$
is an isomorphism where $V$ and $W$ are finite dimensional vector spaces. Let's fix basis $\{w_1,\dots,w_m\}$, $\{v_1,\dots,v_m\}$, and $\{\alpha_1,\dots,\alpha_m\}$ for $W$, $V$, and $V^*$ correspondingly where $\{\alpha_i\}$ is a dual basis for $\{v_i\}$. Next, let's define $\phi$ on basis tensors $\alpha_i\otimes w_j\in V^*\otimes W$ via
$$\phi(\alpha_i\otimes w_j)=f_{\alpha_i}(w_j)$$
where $f_{\alpha_i}(w_j)(v)=\alpha_i(v)w_j$ and extend it linearly since every element $x$ of $V^*\otimes W$ can be written as a finite sum of the basis elements i.e. if $x\in V^*\otimes W$, then $x=\sum_{i,j}a_{ij}\alpha_i\otimes w_j$ and
$$\phi(x)=\sum_{i,j}a_{ij}\phi(\alpha_i\otimes w_j)=\sum_{i,j}a_{ij}f_{\alpha_i}(w_j).$$
Next, I claim that it is enough to show that $\ker(\phi)=0$ since $V^*\otimes W$ and $Hom(V,W)$ have the same dimension and $\phi$ is a linear map (rank-nullity Theorem).
So, let's show that $\ker(\phi)=0$. We can do that by fixing the basis for $V$, $W$, and $V^*$ and showing that if $\phi(x)=0$ then $x=0$ (Details are skipped due to computations).
Does it make sense?
A follow-up question: Do we have an isomorphism if we take either of these spaces to be infinite dimensional? What would we do in that case?