In this study, we report the synthesis of Cu nanoparticle modified dithiocarbamate (DTC)-functionalized magnetic graphene oxide (GO) nanocatalyst through a one-pot three component reaction. It has an excellent affinity for copper nanoparticles due to its DTC ligand amide motif. The structure of the synthesized catalysts was confirmed by using FT-IR, TGA, CHNS, SEM, XRD, EDS mapping, and ICP. The catalytic activity of the synthesized nanocatalyst was investigated in Ullmann cross-coupling reaction for the synthesis of N-aryl amines, which resulted in high reaction yields, easy workup, and short reaction times. The catalyst is separated easily by a magnetic field and can be reused for at least five successive runs without significant loss of catalytic activity. The nature of the supported DTC on the GO’s surface improved the catalytic activity of the graphene, provided homogeneity to the catalyst, and enhanced the capability of coordination with copper ions. Facile catalyst recovery and reusability, simple setup procedure, generality of the method and high turnover number (TON) make this procedure an environmentally benign approach for preparing the titled compounds. Based on the findings of this study, it appears that the catalytic system introduced can be used to prepare other beneficial heterocyclic compounds.