Nitrogen-doped reduced graphene oxide (NRGO) stabilized copper nanoparticles are designed to assist Cu(i)-catalyzed Huisgen [3+2] cycloaddition "click" chemistry (CuAAC). This study demonstrates a robust route for the synthesis of vastly dispersed heterogeneous catalysts (NRGO/Cu2O), achieving CuAAC at low temperature without any external additive (oxidizing/reducing agent) with high stability and recyclability. Underlying mechanisms are analysed using DFT calculations, confirming the experimental results.