DonAntonio already touched linearity and injectivity questions. For surjectivity, you seem to be proving injectivity instead. However, to correctly prove surjectivity, you are going to need to use a dimension-counting argument. This is because, if $W$ is infinite-dimensional and $V\neq 0$, then $$\dim_\mathbb{K}\big(\mathcal{L}(V,W)\big)<\dim_\mathbb{K}\big(\mathcal{L}(W^*,V^*)\big)\,,$$
where $\mathbb{K}$ is the ground field. However, the dual map $\phi:\mathcal{L}(V,W)\to\mathcal{L}(W^*,V^*)$ is still an injective linear map, regardless of the dimensions of $V$ and $W$. The proofs of linearity and injectivity are essentially unchanged.
Since $V$ and $W$ in the problem statement are both finite-dimensional,
$$\dim_\mathbb{K}\big(\mathcal{L}(V,W)\big)=\dim_\mathbb{K}(V)\,\dim_\mathbb{K}(W)=\dim_\mathbb{K}(W^*)\,\dim_\mathbb{K}(V^*)=\dim_\mathbb{K}\big(\mathcal{L}(W^*,V^*)\big)\,.$$
Thus, any injective linear map from $\mathcal{L}(V,W)$ to $\mathcal{L}(W^*,V^*)$ is automatically surjective, whence bijective.
Interestingly, if $W$ is finite-dimensional and $V$ is infinite-dimensional, the map $\phi$ is still an isomorphism. We are left to show that $\phi$ is surjective. To show this, let $S:W^*\to V^*$ be a linear map. Let $n:=\dim_\mathbb{K}(W)$. Pick a basis $\{w_1,w_2,\ldots,w_n\}$ of $W$, along with the dual basis $\{f_1,f_2,\ldots,f_n\}$ of $W^*$ (i.e., $f_i(w_j)=\delta_{i,j}$ for $i,j=1,2,\ldots,n$, where $\delta$ is the Kronecker delta). For each $w\in W$, write $w^{**}\in W^{**}$ for its double dual. Ergo, we see that $S$ takes the form $$S=\sum_{i=1}^n\,e_i\otimes w_i^{**}$$
for some $e_1,e_2,\ldots,e_n\in V^*$ (namely, $e_i:=S(f_i)$ for $i=1,2,\ldots,n$). Define
$$T:=\sum_{i=1}^n\,w_i\otimes e_i\,.$$
Then, for all $j=1,2,\ldots,n$ and $v\in V$, we have
$$\big(T^*(f_j)\big)(v)=f_j\big(T(v)\big)=f_j\left(\sum_{i=1}^n\,e_i(v)\,w_i\right)=\sum_{i=1}^n\,e_i(v)\,f_j(w_i)=\sum_{i=1}^n\,e_i(v)\,\delta_{i,j}=e_j(v)\,.$$
However, as $e_j=S(f_j)$, we get
$$\big(S(f_j)\big)(v)=e_j(v)$$
for all $j=1,2,\ldots,n$ and $v\in V$. This proves that $S(f_j)=T^*(f_j)$ for $j=1,2,\ldots,n$. Because $f_1,f_2,\ldots,f_n$ span $W^*$, we get $S=T^*=\phi(T)$. Therefore, $\phi$ is surjective whenever $W$ is finite-dimensional. (Consequently, the dual map $\phi:\mathcal{L}(V,W)\to\mathcal{L}(W^*,V^*)$ is an isomorphism if and only if $W$ is finite-dimensional or $V=0$.)