The present work demonstrates the synthesis of a hybrid accepter material containing amino-functionalized graphene oxide (GO) and an inorganic semiconducting material, cadmium selenide (CdSe). First, amino-functionalized graphene was synthesized and then nanocrystals (NCs) of CdSe were in situ grown in the functionalized-(GO) matrix named f-GCdSe. Structural studies such as x-ray diffraction, and a scanning electron microscopic were employed to investigate the growth of CdSe NCs in the graphene matrix. To understand the charge generation and transfer process at the donor/acceptor interface, the absorption, photoluminescence (PL), and transient absorption spectroscopic (TAS) studies have been carried out in poly(3-hexylthiophene) (P3HT)/f-GCdSe thin films. PL quenching in P3HT/f-GCdSe thin film suggests that charge transfer takes place at the donor/acceptor interface. TAS shows higher optical density and long lived free carriers for P3HT/f-GCdSe thin film. These results suggest that f-GCdSe is an excellent electron–acceptor material for organic photovoltaic devices.