Photoelectric properties of a novel poly[2-methoxy-5-(2-ethylhexyloxy-p-phenylenevinylen)] (MEH-PPV)/perfluoro-zincphthalocyanine (F16ZnPc) planar heterojunction provided with BCP and MoO3 buffer layers sandwiched between indium tin oxide (ITO) and Ag are shown. Efficient photogeneration of charge carriers at this junction is observed. Effect of bathocuproine (BCP) and MoO3 buffer layers on the performance of cells is analysed. Mechanisms of injection, generation, trapping and recombination of charge carriers in the dark as well as under illumination are discussed. Reliable exciton diffusion length in the F16ZnPc of (18 ± 7) nm is evaluated.