In order to enhance the sunlight-driven photo-Fenton catalytic performance in neutral solution, a novel 2D/2D FeOCl/graphite oxide (GO) heterojunction has been successfully prepared for the first time. This FeOCl/GO shows remarkable enhanced photo-Fenton catalytic activity and stability. Activity measurement results revealed that the prepared FeOCl/GO (1 wt%) catalyst shows the maximum activity for degradation compared with the other prepared catalysts. The degradation constant of FeOCl/GO (1 wt% of GO in FeOCl/GO) is 5.3 times that of FeOCl. The cycling degradation experiments indicate that the FeOCl/GO can be successively used for four consecutive cycles with excellent catalytic activity. The double-transfer mechanism and interfacial electric field for the enhanced photo-Fenton catalytic activity of FeOCl/GO are proposed, which promote the accelerated separation efficient of photoinduced electron–hole pairs. The study has gone some way towards enhancing our understanding of the novel photo-Fenton catalyst for application in an environmental crisis.