Two new dioxovanadium(V) complexes, [VO2L¹] (1) and [VO2L²]2 (2), where L¹ and L² are the deprotonated forms of 4-chloro-2-[(2-piperidin-1-ylethylimino) methyl]phenol and 2-ethoxy-6-[(2-ethylaminoethylimino)methyl]phenol, respectively, have been synthesized and characterized by i.r. spectra and single crystal X-ray diffraction. Complex (1) is a mononuclear dioxovanadium complex, with the V atom five-coordinate in a distorted square pyramidal geometry. Complex (2) is a dinuclear dioxovanadium complex, with the V atom six-coordinate in an octahedral geometry. The V---V distance is 3.096(2) A. The hydrogen bonds among the Schiff base ligands can influence the structures of the vanadium complexes.