I am assuming that the question is about $f_i=e_i^*$.
Existence:
The map $ev:V\to V^{**}$ is an isomorphism (is injective and both spaces have the same dimension). Let $g_1,\cdots,g_n$ be the dual basis of $\{f_i\}$. This is easy to construct since you can define your morphisms $g_i$ in a basis. Now, put $e_i=ev^{-1}(g_i)$. The set $\{e_1,\cdots,e_n\}$ is a basis of $V$ since $ev$ is an isomorphism. Let us show that its dual basis is $\{f_1,\cdots,f_n\}$:
$$
f_j(e_i)=ev(e_i)(f_j)=g_i(f_j)=\delta_{ij}.
$$
Uniqueness:
Let $e'_i$ be another predual basis and write $e'_i=\sum a_{ij}e_j$. Applying $f_k$ in both sides of the equation we get
$$
\delta_{ik}=f_k(e'_i)=\sum a_{ij}f_k(e_j)=\sum a_{ij}\delta_{jk}=a_{ik},
$$
so that $e'_i=e_i$.