Several catalytic reactions such as Ullmann, Chan–Lam, Huisgen 1,3-dipolar cycloaddition, [2 + 3] cycloaddition, condensation, and coupling reactions under suitable conditions have been used for the synthesis of fundamental structures containing a carbon–nitrogen (C–N) bond. Graphene oxide (GO) and its derivatives as heterogeneous catalysts have attracted considerable attention for the synthesis of organic building blocks. Loading of GO derivatives with copper complexes or nanoparticles, as one of the most abundant and low toxic transition metals, allowed to design new composites with predominant ability to C–N bond formation. In this review article, we present a comprehensive overview on the synthesis of building blocks containing a C–N bond such as amines, triazoles, tetrazoles, propargyl amines, imidazoles, and benzodiazepines using GO derivatives loaded with copper complexes or nanoparticles. © 2021 John Wiley and Sons, Ltd.