Yes, this is possible, u + w creates a new Expression which can be used in a variational problem.
However, if you want to have it as a Function, then you need to project it to a finite element space:
v = project(u + w, V)
If you know the two Functions are in the same space, you could also directly sum the degrees of freedom:
v = Function(V)
v.vector()[:] = u.vector()[:]
v.vector() += w.vector()
(Example code is untested Python but should work with minor modifications in C++.)