A comprehensive investigation was performed to enhance the catalytic performance of Cu/Cu2O nanoparticles via introduction of graphene as a beneficial support for two organic transformations viz. reduction of nitrophenols to aminophenols and ring opening of epoxides with amines. Cu/Cu2O@Graphene nanostructures bestowed significant catalytic features owing to the increased accessibility of catalytically active surface sites and the augmented efficacy with increase in graphene content was validated by enhanced specific surface area. The reaction routes were traced by performing computations within DFT formalism. Cu/Cu2O nanocatalyst guided the reactions through a barrierless transition state and the enhanced efficacy of nanoparticles supported on graphene was demonstrated by their favorable adsorption on nanosurface with interfacial charge transfer between the two. Interestingly, the catalytic reactions provide significant contribution to environmental sustainability with the view of conversion of recalcitrant pollutants to useful compounds. The present study outlines the versatile potential of graphene based nanostructures in catalytic reactions. (C) 2019 Elsevier Inc. All rights reserved.