To enhance the Fenton catalytic performance in a neutral solution under indoor sunlight, a novel FeOCl/polyoxometalate (POM) (FeOCI/POM-W and FeOCl/POM-Mo) composite was successfully synthesized for the first time, which shows significantly improved Fenton catalytic activity and stability for phenol degradation compared with FeOCl. Furthermore, the degradation constants (k) of FeOCl/POM-Mo (0.08 min(-1)) and FeOCl/POM-W (0.06 min(-1)) are a factor of 4 and 3 times greater than that of FeOCl (0.02 min(-1)), respectively. The enhanced catalytic activity is attributed to the formation of FeOCl/POM heterojunctions, which results in efficient separation of photoinduced electron-hole pairs and electron transfer from POM to FeOCl. Density functional theory calculations indicate a strong interface interaction of Fe-O-Mo and Fe-O-W in the FeOCl/POM heterojunctions. A Z-scheme mechanism for FeOCl/POM-Mo and a double-transfer mechanism for FeOCl/POM-W are proposed for the enhanced catalytic performance. This study sheds new light on the design and fabrication of high-performance photo Fenton catalysts to overcome the environmental crisis.