Evolution in the atomic structure, bonding characteristics, stability, and the spin magnetic moment of neutral and cationic AgnV clusters has been investigated using first principles density functional approach with gradient corrected functional. It is shown that at small sizes, the V 4s states hybridize with Ag states to form 1S and 1P like superatomic orbitals, while the 3d states are localized on V giving the V atom an effective valence of 1 or 2. Starting from Ag8V(+), the V 3d states begin to participate in the bonding by hybridizing with the nearly free electron gas to form 1D superatomic orbitals increasing the V atom effective valence towards 5. For the cationic clusters, this changing valence results in three shell closures that lead to stable species. These occur for cationic clusters containing 5, 7, and 14 Ag atoms. The first two stable species correspond to filled 1S and 1P shells in two and three dimensions with a valence of 2 for V, while the closure at 14 Ag atoms correspond to filled 1S, 1P, and 1D shells with V site exhibiting a valence of 5. The transition from filled 1S, 1P shells to filled 1S, 1P, and 1D shells is confirmed by a quenching of the spin magnetic moment. The theoretical findings are consistent with the observed drops in intensity in the mass spectrum of AgnV+ clusters after 5, 7 and 14 Ag atoms.