Four oxovanadium(IV) complexes, namely [VO(desa-met)(phen)]ÁMeOHÁ2H 2 O (1) (desa-met = Schiff base derived from 4-(diethylamino)salicylaldehyde and DLmethionine, phen = 1,10-phenanthroline), [VO(o-van-met)-(phen)]ÁMeOHÁCH 2 Cl 2 Á3H 2 O (2) (o-van-met = Schiff base derived from o-vanillin and DL-methionine), [VO(dtbsnapa)(phen)]Á2H 2 O (3) (dtbs-napa = Schiff base derived from 3,5-di-tert-butyl salicylaldehyde and 3-(1-naphthyl)-Lalanine) and [VO(hyna-napa)(phen)]Á1.5H 2 O (4) (hynanapa = Schiff base derived from 2-hydroxy-1-naphthaldehyde and 3-(1-naphthyl)-L-alanine), were synthesized and characterized by IR, HRMS, UV-vis spectra, molar conductance and single-crystal X-ray diffraction (XRD). X-ray structural analysis showed that the V(IV) atoms in all four complexes are six-coordinated in a distorted octahedral environment. In the crystals of complexes 1 and 2, p-p stacking interactions together with hydrogen bonds connect the molecular units into 2D networks. Meanwhile, CH-p stacking interactions are observed between the aromatic rings in the crystals of 1 and 4, while the p-p stacking interactions between aromatic rings in the crystals of 2 and 3 are arranged with a face-to-face mode. The in vitro anticancer activities of these complexes against A-549 and HeGp2 cells were tested by MTT assay.