A B3LYP/6-31G* study on geometrical, thermodynamic and electronic properties of the VOx+ and VOx (x = 1-4) systems in the ground and some excited electronic states has been carried out to obtain the most stable structures, vibrational frequencies and reaction energies of the possible decomposition channels. The most energetically favorable conformations of VO2+ ((1)A(l)) and VO2 ((2)A(l)) are bent structures while VO3+ ((1)A') and VO3 ((1)A') arrangements have pyramidal geometries with C-s symmetry. VO4+ ((3)A) and VO4 (B-2(2)) ground state render C-1 and C-2v symmetries, respectively. Electron localization function (ELF) has been used to discuss and analyze the nature of the bonding.