A novel heterogeneous composite material based on reduced graphene oxide (rGO) and bismuth vanadate (BiVO4) was prepared and characterized by various techniques such as powder XRD, HRTEM, EADX, UV–Vis‐DRS, FT‐IR, Raman, BET and XPS analyses. The characterization results reveal that the rGO well decorated by BiVO4. The electrochemical impedance spectroscopy (EIS) shows the increasing of charge transfer of rGO/BiVO4 in presence of light irradiation. In this research, the pure BiVO4 and rGO/BiVO4 composite have been explored for photocatalytic reduction of nitroarenes. Among the prepared nanocomposites, rGO loaded with 10% BiVO4 catalyst (noted as rGO/BiVO4–10%) shows the best performance for the photo‐reduction of various nitroaromatic molecules to their corresponding amine compounds under visible‐light irradiation at room temperature. The catalyst exhibited in particular excellent photocatalytic activity for the conversion of 1,4‐dinitrobenzene to 4‐nitroanilline (100% conversion) in 20 min, 4‐chloronitrobenzene to 4‐chloroaniline and 2‐nitrophenol to 2‐aminophenol (100% conversion) in only 30 min. In addition, the conversion of 4‐bromonitrobenzene, 4‐iodonitrobenzene to their corresponding amine compounds (100% conversion) was achieved in 60 min. The catalyst was recovered for several times and reused without decreasing of its efficiency.