State of the art CASSCF and CASPT2 calculations have been performed to elucidate the nature of the electronic transitions observed in the experimental spectrum of the octacyanomolybdate(V) cation. Assuming a triangular dodecahedral structure for this complex gives a convincing agreement between theory and experiment. All absorption bands are assigned to low-lying charge-transfer transitions involving excitations from ligand orbitals to 4d(x2-y2). The calculated molecular orbitals reveal weak pi interactions between the metal and ligand orbitals, compared to much stronger a interactions. This calculated electronic structure substantiates the previous hypothesis concerning the giant spin ground states of magnetic clusters and networks containing Mo(CN)(8)(3-) as a constituent part.