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We have investigated the electronic transport and transient photovoltaic properties on the La2/3Ca1/3MnO3/Nb (0.05 wt. %):SrTiO3 heterojunction as the temperature increasing from 293 to 623 K. We observed temperature-dependent reversal of the rectifying polarity in the junction with increasing temperature. Temperature also shows effective affection to the transient photosensitivity and response time. On the basis of the results, we propose a possible model involving the change in barrier height and/or width for the carrier conduction at the junction interface induced by the electrochemical migration of oxygen vacancies as the mechanism. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4737256]