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Vanadium oxide (VOx) is a promising candidate as a material for smart windows, and 0.7 wt% Nb-doped SrTiO3 (NSTO) is frequently used in electrodes for electro-optic devices. Here, we demonstrate that a rectifying VOx/Nb: SrTiO3 heterojunction has a photovoltaic response. It can be used in thermochromic photovoltaic modulating devices. The crystalline structure and electrical characteristics of VOx thin film deposited on NSTO were investigated. It was found that an asymmetric hysteresis current between increasing and decreasing voltages occurs at 80, 300 and 360 K. The photovoltaic effect was observed under irradiation by a pulsed laser. [ABSTRACT FROM AUTHOR]