Let me first cite a theorem due to Frobenius:

Let $G$ be a finite group, with $H$ a subgroup. Suppose that for every $g\not\in H$, we have $H\cap gHg^{-1}=(1)$. Then $$N:=(1)\cup(G\setminus\bigcup_{g\in G}gHg^{-1})$$ is a normal subgroup of $G$.

The proof is fascinating. One never proves directly that $N$ is stable under the product and the inversion. Instead, one constructs a complex character $\chi$ over $G$, with the property that $\chi(g)=\chi(1)$ if and only if $g\in N$. This ensures (using the equality case in the triangle inequality) that the corresponding representation $\rho$ satisfies $\rho(g)=1$ if and only if $g\in N$. Hence $N=\ker \rho$ is a subgroup, a normal one!

Does anyone know an other example where a subset $S$ of a finite group $G$ is proven to be a subgroup (perhaps a normal one) by using character theory? Is there any analogous situation when $G$ is infinite, say locally compact or compact?