Sure -- Gram Schmidt orthogonalization and the change of basis theorem.
Reduction: for any vector $v$ of norm $1$, there's a matrix $M_v$ taking $e_1$ to $v$. I'll prove this in a moment.
Once you accept that, the general theorem is easy: to take $u$ to $w$, you let $h = u / \| u \|$ and $k = w / \| w \|$, and use the matrix $M_k \cdot (M_h)^{-1}$. (For $\| u \| = 0$, any matrix will work.)
To prove the reduced claim:
Apply gram-schmidt to the ordered set
$$v, e_1, e_2, \ldots, e_n$$
discarding any vector that becomes zero after projection on the prior subspace; the result is a list of vectors
$$
v, a_2, \ldots, a_n
$$
that are orthonormal. The matrix $M$ whose columns are these vectors in order is a rotation taking $e_1$ to $v$.
Notice that this implies something stronger than your claim: not only is there an orthogonal matrix taking $v$ to $w$, but there's one of determinant $+1$ (i.e., a rotation).