Hybrid solar cells based on CdSe nanoparticles and a PPV-type polymer containing fluorene and thiophene units (PFT) were investigated. The CdSe/PFT devices showed very low photocurrent and fill factor values, which was attributed to the poor charge transport in the TOPO-capped CdSe nanoparticle phase. Thus, ternary systems based on mixtures of PFT/CdSe and the fullerene derivative PCBM were investigated. The CdSe: PCBM ratio was varied, and nanoparticles with different sizes were also used. It was observed that for the optimized composition of 20 wt% PFT + 40 wt% CdSe + 40 wt% PCBM the devices presented higher photocurrents and efficiencies. The photophysical and electrochemical properties and microscopy images (AFM and HRTEM) of the ternary systems were systematically investigated to elucidate the mechanism of action of the inorganic nanoparticles in these ternary hybrid devices.