The optical and photovoltaic properties of two-component TPP–Yt0.95Er0.05VO4 films prepared by the spincoating method are for the first time studied. A 30% increase in the photovoltage (PV) of TPP: Yt0.95Er0.05VO4 = 3: 2 films on silicon carbide (SiC) supports as compared to TPP one-component films is observed. In contrast, for films on tin dioxide (SnO2) supports, the PV drops by 35–96% as the TPP content in the film decreases from 80 to 20%. The properties of the films are monitored by atomic force microscopy. The highest roughness of the films corresponds to a 40–60% TPP content. © 2016, Pleiades Publishing, Ltd.