A nitrogen-doped reduced graphene oxide/Fe3O4 composite (NGO-Fe3O4) was prepared through the simplified hydrothermal and deposition-precipitation method and characterized by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The degradation efficiency of oxytetracycline (OTC) by NGO-Fe3O4 activated peroxodisulfate (PDS) under visible light irradiation was studied. The degradation efficiency reached 100% within 32.5 min (the initial OTC concentration 50 mg L−1 and PDS 1 mM; [NGO-Fe3O4]:[ PDS] = 4:1; pH = 3.0). No apparent decrease in degradation efficiency was observed after five cycles. SO4−· and ·OH were the main active oxides for OTC degradation in this system. Moreover, four degradation pathways were proposed, namely hydroxylation, dehydration, decarbonylation and demethylation according to the analysis results of high-performance liquid chromatography mass spectrometry.