Precisely if $\{v_1, \ldots, v_n\}$ is an orthonormal basis. Indeed, given $u \in \Bbb R^n$, we may write $u = \sum_{i=1}^n c_i v_i$. Now for each $j$, $\langle u, v_j \rangle = \sum_{i=1}^n c_i \langle v_i, v_j \rangle = c_j \langle v_j,v_j \rangle = c_j$ and it follows that $u = \sum_{i=1}^n \langle u,v_i \rangle v_i$.
Conversely, if for each $u$ it holds that $u = \sum_{i=1}^n \langle u, v_i \rangle v_i$, then given $j$, we have for $u = v_j$:
$$v_j = \sum_{i=1}^n \langle v_j , v_i \rangle v_i \tag1$$
It follows that:
$$\|v_j\|^2 = \langle v_j, v_j \rangle = \langle \sum_{i=1}^n \langle v_j , v_i \rangle v_i, v_j\rangle =\sum_{i=1}^n \langle v_i ,v_j \rangle ^2 = \|v_j\|^2 + \sum_{i \neq j} \langle v_i ,v_j \rangle ^2$$
So for each $i \neq j$, $\langle v_i, v_j \rangle = 0$, and returning to $(1)$, we see that $v_j = \|v_j\|^2 v_j$, so $v_j = 0$ or $\|v_j\|^2 =1$.
By the assumption that each $u$ can be written as $\sum_{i=1}^n \langle u,v_i \rangle v_i$, $\{v_1, \ldots, v_n\}$ spans $\Bbb R^n$, so it must be a basis, hence each $v_i$ is non-zero, and it follows that for all $j$, $\|v_j\|^2 = 1$ i.e. $\|v_j\| = 1$.