Two new oxidovanadium(V) complexes, [VO2L1] (1) and [V2O2(μ-O)2L2)] (2), where L1 and L2 are the deprotonated form of 5-bromo-2-(((2-(pyrrolidin-1-yl)ethyl)imino)methyl)phenol (HL1) and 5-bromo-2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol (HL2), respectively, have been synthesized and structurally characterized by physico-chemical methods and single crystal X-ray determination. X-ray analysis indicates that the V atom in complex 1 is in square pyramidal coordination, and those in complex 2 are in octahedral coordination. Crystal structures of the complexes are stabilized by hydrogen bonds. The catalytic property for epoxidation of styrene by the complexes was evaluated.