Doping with graphene nanosheets has attracted significant interest from researchers to enhance the structure and properties of nanomaterials because of graphene's unique properties and broad and essential applications. The study aims to focus on the effect of functional groups of both polymers and nanomaterials to fabricate a new nanocomposite consisting of poly (acrylamide) (PAAm) with poly (vinyl alcohol) (PVA) before and after the addition of graphene oxide nanosheets (GO) and studying its structural and optical properties. The developed method (dissolving with water, mixing, sonication, and casting) showed success in fabricating new nanocomposites for the first time by mixing these components with a ratio of 4.5: 4.5: 1 as percentages (PAAm: PVA: GO). Samples showed homogeneity of the polymer mixtures with each other and the excellent dispersion of graphene oxide nanosheets in the new polymer nanocomposite as exhibited by optical microscopy. The spectra of the Fourier infrared spectroscopy showed the strong interfacial interaction of the two polymers in the polymeric mixture with GO nanoparticles as nanocomposites. Also, X-ray diffraction showed shifting in some peak positions and increased crystallization of the polymers in the nanocomposites. The nanocomposites showed a notable improvement in the optical properties due to doping the polymeric mixture with graphene oxide compared with their blended polymers. The energy gap also significantly decreased after the contribution of graphene oxide up to 136% and 900% for the permitted and prohibited direct transfers, respectively. These results exposed promising nanocomposites for widespread applications such as solar cells. [ABSTRACT FROM AUTHOR]