This work entails a novel and simple chemical method for preparation of silver and reduced graphene oxide nanocomposite (Ag@rGO NCs). In nanocomposite fabrication, the silver salt was reduced through Eriochrome Black T (EBT) and Methylene Orange (MO) respectively in the presence of graphene oxide. The mechanism of interaction was understood by simulating the system using first-principle Density Functional Theory approach. The formation of silver nanoparticles was confirmed through UV–visible spectroscopy by observing the plasmonic peak. By X-Ray Diffraction (XRD) analysis, the crystallite size of silver nanoparticles was calculated to be 9.83 nm and 12.5 nm respectively, for two nanocomposites. Statistically, spherical surface morphology and average particles diameter of silver was assessed to be 38 nm and 42 nm from scanning electron microscopy (SEM) analysis. Energy dispersive spectroscopy (EDS) confirmed the presence of silver in the nanocomposites. Fourier Transform Infrared (FTIR) and RAMAN Spectroscopy confirmed the interaction mechanism of GO and Ag NPs by changes in surface groups. In photocatalysis, the dye degradation efficiency of Ag@rGO NCs have been studied against Methylene Blue (MB) and found to be 69.7% and 87.9% approximately.