An improved hybrid solar cell was obtained by focusing on the effects of ligand for CdSe nanoparticles, in the active layers. The performance was compared by mixing nanoparticles capped with pyridine or oleic acid for the acceptor material into poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester based active layer. The solar cells with pyridine capped CdSe nanoparticles showed a power conversion efficiency of 2.96% while oleic acid capped CdSe nanoparticles showed 2.85%, under AM 1.5G illumination. Formation of percolation pathways for carrier transport and a reduction in the hopping event resulted in better performance of pyridine capped nanoparticles.