No, it does not. As a simple example, let $G\cong S_3$, $\Omega = G/C_2 \sqcup G/C_2 \sqcup G/C_3$. You can easily check that the corresponding permutation character is isomorphic to the regular character plus two copies of the trivial. In other words,
$\mathbb{C}[G/1] \oplus \mathbb{C}[G/G]^{\oplus 2} \cong \mathbb{C}[G/C_3] \oplus \mathbb{C}[G/C_2]^{\oplus 2}$.

One systematic source of such counterexamples are Brauer relations in which the regular set $G/1$ enters with non-zero coefficient, of which both Tim's and my answer are particular examples (for more on Brauer relations see e.g. [this MO question][1], as well as google).


  [1]: https://mathoverflow.net/questions/92637/generalizations-applications-of-a-formula-for-the-dedekind-zeta-function/92649#92649