One has to be careful, because a finite vector space can well be the union of finitely many proper subspaces. For instance the vector space of dimension two over the field with two elements is the union of three subspaces of dimension one.
Note first that each $V_i$ can be assumed to be one-dimensional. Add the subspace $V_{0} = \{ (0, a) : a \in \Bbb{C} \}$ to the $V_{i}$ for good measure, and suppose each $V_i \ne V_0$ for $i \ne 0$.
Then in each $V_i$ (with $i \ne 0$) there is a unique element of the form $(1, a_i)$. Choose an element $a \notin \{ a_i : i \in 1, \dots, 100 \}$. (Here of course we are using the fact that $\Bbb{C}$ is infinite.) Then $(1, a) \notin \bigcup_{i=0}^{100} V_i$, so $V \ne \bigcup_{i=0}^{100} V_i$.
So this works for any finite number of subspaces, and any infinite field.