Vanadium (II) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium (III) complexes with bi-dentate O, N-chelating heteroarylalkenol ligands (DmoxCH=COCF3, PyCH=COCF3 and PyN=COCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. Chemical identity of V(III) complexes and their redox behaviour was unambiguously established by single crystal X-ray diffraction studies, cyclovoltammetry, spectrometric studies and DFT calculations. Transformation to metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures respectively.