We have optimized the geometrical structures of the vanadium clusters Vn and discussed their evolution with cluster sizes in the average nearest-neighbor distances, coordination numbers, binding energies, ionization potential, electron affinities, density of states, valence band width, and magnetic moments using the density functional theory.We found that the clusters from V2 to V9 have distinctly molecular behaviour with dramatic size variations; V13, V15, and V19 are the transition regions from the molecular features to the bulk structures, and V27 and V51 possess almost the bulk properties.