Suppose the subspaces are S1,S2,S3.....Sk
Take a from S1, b from S2....k from Sk
then a+b+....k belongs to V and union of all subspaces.
By the definition of union, a+b+....k must belong to atleast one of the subspace which will make it equal to V.
Is this proof correct? Or am I missing something?
Actually, if a vector space over a field $F$ is the union of $k$ proper subspaces, then $|F|<k$. So if the field is infinite, one of the subspaces is equal to $V$. This result is known as the avoidance lemma for subspaces.
For a proof you can take a look at my answer to this closely related question