This work describes the synthesis and characterization of a heterogeneous catalyst consisting of piperazine-functionalized reduced graphene oxide decorated with Fe3O4 nanoparticles (Fe3O4@rGO-NH), and the study of its catalytic activity as a magnetic heterogeneous catalyst for the Pechmann synthesis of coumarins. Catalyst Fe3O4@rGO-NH was fully characterized by various techniques, including IR, XRD, TEM, VSM, TGA, and elemental analysis. Then, the catalyst was used as an efficient and easy-separable heterogeneous catalyst for the solvent-free synthesis of some coumarins by Pechmann reaction. The reaction was optimized in terms of reaction time and temperature, catalyst dosage, and the presence/absence of the solvent. Finally, the reusability of the catalyst was studied.