A $R$-algebra $A$ is a group algebra over $R$ if and only if there exists a $R$-module basis of $A$, which is also central and a subgroup of $R^*$$A^*$. Of course, this is trivial, but I don't think that there is a nice characterization.
Observe that some $R$-algebras $A$ don't have any $R$-homomorphism $A \to R$ at all. However, group algebras admit the augmentation map $R[G] \to R$. Besides, the diagonal map $G \to G \times G$ induces $R[G] \to R[G] \otimes R[G]$ and endow $R[G]$ with the structure of a coalgebra.