This answer is just to show how much of the result generalizes to arbitrary ground fields of characteristic $0$, and along the way gives the result mentioned by Paul Garrett (in a comment to Tobias Kildetoft's canonical answer) that over the real numbers, the Killing form restricted to a maximal split toral subalgebra is actually positive definite i.e. has an orthonormal basis in the strongest sense of the word.
Let $\mathfrak g$ be a semisimple Lie algebra over a field $K$ of characteristic $0$. Let $\mathfrak s \subset \mathfrak g$ be a maximal split toral subalgebra (which in general is not quite a Cartan subalgebra).
Then with respect to such $\mathfrak s$, generalizing the usual split case we have a decomposition
$$\mathfrak g = \mathfrak g_0 \oplus \bigoplus_{\alpha \in R} \mathfrak g_\alpha$$
where $\mathfrak g_\alpha = \{x \in \mathfrak g: [s,x]=\alpha(s)x \text{ for all } s \in \mathfrak s\}$, and $R$ is a finite subset of the dual $\mathfrak s^*$. Indeed one shows as in the split case that $R$ spans $\mathfrak s^*$. (One also shows that $R$ is (either empty or) a root system, just possibly non-reduced; but one might show this after what comes next here; it is not needed in the following.)
Now elementary considerations show that with respect to the Killing form $\kappa$ (which is non-degenerate on $\mathfrak g$ by Cartan's criterion), for all $\alpha, \beta \in R \cup \{0\}$ we have $\mathfrak g_\alpha \perp \mathfrak g_\beta$ unless $\beta =-\alpha$. This implies that the restriction of $\kappa$ to $\mathfrak g_0 \times \mathfrak g_0$ is non-degenerate as well.
In the split case, where $\mathfrak s$ is a Cartan subalgebra and hence equals its own centralizer $\mathfrak g_0 = C_\mathfrak g(\mathfrak s)$, we have now shown the Killing form restricted to the Cartan is non-degenerate. This is the case e.g. if $K$ is algebraically closed, so in that case now go to Tobias' answer.
However, in general $\mathfrak g_0 = C_\mathfrak g(\mathfrak s)$ will be bigger than $\mathfrak s$, and as further deviation from the well-known split case, the root spaces $\mathfrak g_\alpha$ can have dimension $\ge 2$. But it still follows more or less from definitions that the restriction of $\kappa$ to $\mathfrak s \times \mathfrak s$ is given by
$$\kappa(s_1, s_2) = \sum_{\alpha \in R} \dim_K(\mathfrak g_\alpha) \alpha(s_1)\alpha(s_2)$$
From this we conclude:
If $K =\mathbb R$ or a similar (namely, ordered) field, we are done again. Because for any $s \in \mathfrak s \setminus \{0\}$, by the above formula $\kappa(s,s)$ is a sum of squares times positive integers, at least one summand being non-zero, so it is positive, and we have shown a stronger result: that the restriction of $\kappa$ to $\mathfrak s \times \mathfrak s$ is positive definite. For $K=\mathbb R$, Gram-Schmidt will do the rest. (Note that e.g. over $K=\mathbb Q$, we cannot expect an orthonormal basis because scaling might not work.)
In general, the restriction of $\kappa$ to $\mathfrak s \times \mathfrak s$ is still non-degenerate. I would like to see a more direct proof for that. The one I have (which is spread out in lemma 3.1.9, 3.1.10 and proposition 3.1.11 in my thesis) needs a bit more input: Namely, first via fine-tuning the Jacobson-Morozov Theorem we construct for each root $\alpha$ an element $H_\alpha \in [\mathfrak g_\alpha, \mathfrak g_{-\alpha}] \cap \mathfrak s$ such that $\alpha(H_\alpha)=2$; one then shows that the $(H_\alpha)_{\alpha \in R}$ generate $\mathfrak s$, that $\kappa(H_\alpha, H_\alpha)$ is a positive integer (follows from the formula above), and with some root string considerations and $\mathfrak{sl}_2$-representations, that $\alpha(s) = 0 \implies \kappa(s, H_\alpha)=0$. This last fact immediately gives the seemingly much stronger
$$ \alpha(s)= 2 \dfrac{\kappa(H_\alpha, s)}{\kappa(H_\alpha, H_\alpha)} $$
for all $s \in \mathfrak s, \alpha \in R$. And this, finally, implies that $\kappa$ is non-degenerate, because otherwise there would be an $s \in \mathfrak s \setminus \{0\}$ such that $\alpha(s)=0$ for all $\alpha \in R$, contradicting the fact that those span $\mathfrak s^*$.