Let $R$ be an arbitrary associative ring with identity. When does there exist a group $G$ and a field $F$ such that $F[G] = R$?
Do we obtain more rings as $F[G]$ if we loosen the condition that $F$ be a field? When can we get $G$ to be a finite group?
There seem to be some obvious restrictions: The characteristic of $F$ is equal to that of $R$, for instance. Also, when $F$ and $G$ are finite, then so is $R$. Also, all elements of $G$, considered as a subset of $R$, are units in $R$. If $R$ is commutative, $G$ has to be abelian. But I fail to see much more.
The simplest case, which is already quite complicated, is if $F$ is algebraically closed of characteristic $0$ and $G$ is finite, or equivalently if $R$ is finite dimensional over $F$ (note that $R$ is necessarily an $F$-algebra). Then $F[G]$ is semisimple by Maschke's theorem, and furthermore splits up as a finite product of matrix algebras $M_n(F)$, one for every irreducible representation of $G$ over $F$ of dimension $n$. So in this special case the question reduces to asking:
I don't think there's any hope of a simple answer to this question. Here are some necessary conditions. Note that $|G| = \sum n_i^2$.
For example, $F \times M_2(F)$ is not a group algebra (because $1^2 + 2^2 = 5$ and the only group of order $5$ is $C_5$), but $F \times F \times M_2(F)$ is (it's the group algebra of $S_3 \cong D_3$).