Mo-doped VO2 nanowire array film with good thermochromic properties was prepared by melting-quenching followed by heat treatment in a vacuum. The formation of the new microstructure is related to the cleavage of the oxide lamella along (001) and (100) plane with large interplanar spacing. Mo doping results in the loss of V4+-V4+ pairs and destabilizes the semiconductor phase and consequently lowers the semiconductor-to-metal transition temperature T-c from 64 to 42 degrees C. Because of enhancement of the electron concentration due to the presence of Mo donors, the Fermi level shifts toward the conduction band, resulting in the decrease of activation energy E-a, hence, temperature coefficient of resistance.