As the world demand for energy continue to increase, it is vital to improve renewable energy technologies that will replace conventional fossil fuels. Carbonaceous graphene oxide (GO) is a promising nanomaterial, easy to prepare and scale up to commensurate with industrial requirements. The nanocomposite was prepared in the form of layered structure of GO nanomaterials and poly (3-hexylthiophene) (P3HT) for photovoltaic applications. The X-ray diffraction (XRD) revealed the interaction of P3HT with GO through decrease in lattice spacing. It was evident from scanning electron microscopy (SEM) that the presence of P3HT in GO modified flower like structure to the flaky structures. The interaction of GO with P3HT is presented by various vibrational frequencies in Fourier Transform infrared spectroscopy (FTIR). The increased absorbance and broadening of absorption was observed in the UV-vis spectrum for nanocomposite due to ionic interaction between P3HT and GO. The tunable photoluminescence (PL) measurements showed quenching and shifting of emission spectrum due to charge and energy-transfer. The nanocomposite establish the formation and existence of energy levels upon interaction of GO with P3HT which enhances charge transport. This work provides the direction on coating of thin films for photovoltaic device fabrication. Copyright © 2017 VBRI Press.