Let $k$ be an algebraically closed field whose characteristic is either zero or prime to the order of $G$.
Then the center of the group ring $kG$ has one basis in natural bijective correspondence with the set of irreducible representations of $G$ over $k$, and another basis in natural bijective correspondence with the conjugacy classes of $G$.
Namely:
1) $kG$ is semisimple (this is called Maschke's Theorem) and Artinian, so it is a direct sum of matrix rings over division rings. , hence (because $k$ is algebraically closed) a direct sum of matrix rings over $k$. There is (up to isomorphism) one irreducible representation for each of these matrix rings. Those representations are therefore in natural one-one correspondence with the central idempotents that generate those matrix rings, and these form a basis for the center.
2) For each conjugacy class, we can form the sum of all elements in that conjugacy class. The resulting elements of $kG$ form a basis for the center.
This gives a (non-natural) bijection between irreducible representations and conjugacy classes, because there is a (non-natural) bijection between any two bases for a given finite-dimensional $k$-vector space. I do not see any way you can make this natural.
