A new form of fullerene-capped CdSe nanoparticles (PCBA-capped CdSe NPs), using carboxylate ligands with [60]fullerene capping groups that provides an effective synthetic methodology to attach fullerenes noncovalently to CdSe, are presented for usage in nanotechnology and photoelectric fields. The effective energy transfer in the hybrid material contributes to photoluminescence (PL) quenching of the CdSe moieties. Reported for the first time is the hybrid-polymeric solar cell consisting of P3HT donor and PCBA-capped CdSe acceptor.