The photogeneration mechanism in blends of poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) and poly[oxa-1,4-phenylene-(1-cyano-1,2-vinylene)-(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene)-1,2-(2-cyanovinylene)-1,4-phenylene] (PCNEPV) is investigated. The photocurrent in the MDMO-PPV:PCNEPV blends is strongly dependent on the applied voltage as a result of a low dissociation efficiency of the bound electron–hole pairs. The dissociation efficiency is limited by low carrier mobilities, low dielectric constant, and the strong intermixing of the polymers, leading to a low fill factor and a reduced photocurrent at operating conditions. Additionally, electrons trapped in the PCNEPV phase recombine with the mobile holes in the MDMO-PPV phase at the interface between the two polymers, thereby affecting the open-circuit voltage and increasing the recombination losses. At an intensity of one sun, Langevin recombination of mobile carriers dominates over trap-assisted recombination.