[guided]To prove linear independence, we must show that the only solution to $\sum_{i=1}^k c_i v_i = 0$ is $c_1 = \cdots = c_k = 0$.
The strategy is the same one used in the proof of [Coordinates in an Orthonormal Basis](/theorems/3267): take the inner product with a specific basis vector to "select" one coefficient. Here we take the inner product with $v_j$ to isolate $c_j$.
Suppose $\sum_{i=1}^k c_i v_i = 0$ for scalars $c_1, \ldots, c_k \in \mathbb{R}$. Fix any $j \in \{1, \ldots, k\}$. Taking the inner product of both sides with $v_j$:
\begin{align*}
\langle 0, v_j \rangle &= \left\langle \sum_{i=1}^k c_i\, v_i,\, v_j \right\rangle.
\end{align*}
The left-hand side is $0$ (since $\langle 0, v_j \rangle = 0$ for any $v_j$). On the right-hand side, linearity of the inner product in the first argument gives:
\begin{align*}
0 &= \sum_{i=1}^k c_i\, \langle v_i, v_j \rangle.
\end{align*}
By pairwise orthogonality, $\langle v_i, v_j \rangle = 0$ whenever $i \neq j$. So every term in the sum vanishes except $i = j$:
\begin{align*}
0 &= c_j\, \langle v_j, v_j \rangle = c_j \|v_j\|^2.
\end{align*}
Now we use the hypothesis that $v_j \neq 0$. The inner product is positive definite: $\langle v_j, v_j \rangle > 0$ whenever $v_j \neq 0$. So $\|v_j\|^2 > 0$, and we can divide both sides by $\|v_j\|^2$ to get $c_j = 0$.
Since $j$ was arbitrary, all coefficients are zero. This is exactly the definition of linear independence.
What role does the nonzero hypothesis play? If some $v_j = 0$, then $\|v_j\|^2 = 0$ and the equation $c_j \|v_j\|^2 = 0$ holds for any $c_j$ -- we cannot conclude $c_j = 0$. Indeed, the zero vector is orthogonal to everything, so $\{0, v_2, \ldots, v_k\}$ is pairwise orthogonal but not linearly independent (since $1 \cdot 0 + 0 \cdot v_2 + \cdots + 0 \cdot v_k = 0$ is a non-zero linear relation).[/guided]