The purpose of this study was to investigate the effect of photo-assisted heterogeneous Fenton on p-nitrophenol (PNP) wastewater treatment by a homemade reactor. Supported Fe-Ce/Al2O3 was used as catalyst and H2O2 as an oxidant to treat simulated p-nitrophenol wastewater under ultraviolet light. The effects of H2O2 dosage, catalyst dosage, initial solution pH value, reaction temperature and reaction time on the removal rate of p-nitrophenol in a photo-assisted heterogeneous Fenton system were determined. According to the relation between the concentration of each component and time, the relation curve is fitted, and then the kinetic equation is established. Finally, we obtained the optimum process conditions to achieve the PNP wastewater removal rate of 98.7%. The degradation of the photo-assisted heterogeneous Fenton method conforms to the first-order kinetic model, and the kinetic equation is LnC − LnC0 = −kt. Therefore, photo-assisted heterogeneous Fenton treatment of PNP wastewater is effective and can be used in the treatment of refractory wastewater.