Electronic structures of the hexagonal V 2 AlC and V 2 AlN compounds with Cr 2 AlC-type structure are studied using the full-potential linearized augmented-plane-waves method within the generalized gradient approximation. The results show that the bonding is due to V-d–(C, N)-p and V-d–Al-p hybridizations, and the V-d–Al-p bonds are stronger in V 2 AlN than in V 2 AlC. The analysis of the band structure, charge density and total density-of-states at the Fermi level also indicated that V 2 AlC and V 2 AlN exhibit metallic electrical conductivity and V 2 AlN should be more conductive than V 2 AlC. We also find that the replacement of C with N will result in a more stable crystal structure.