Abstract：BiPO4/α-Fe2O3 hybrid photocatalysts was synthesized by hydrothermally method and characterized by means of X-ray diffraction （XRD）， scanning electron microscope （SEM）， X-ray photoelectron spectroscopy （XPS）， transmission electron microscope （TEM）， UV-VIS reflection spectrometer （DRS）， N2 adsorption-desorption measurement （BET） and photoluminescence spectroscopy （PL）. The styrene degradation efficacy of hybrid catalysts prepared under different conditions and their photocatalytic mechanism were discussed. The results showed that the loading of natural hematite could effectively improve the separation efficiency of BiPO4 photoelectron-hole pair and enhance its photocatalytic activity， when the mass ratio of BiPO4 and α-Fe2O3 precursors was 1∶1，initial solution pH value was 1 and calcination temperature was 300 ℃， its degradation rate with 50 mg·m-3 styrene was 87.9%. The degradation rate only decreased 5.9% after 4 cyclic experiments under the same conditions， confirming its superior stability. Photocatalytic degradation of styrene by hybrid catalysts was mainly caused by photoelectron-hole， oxygen-derived superoxide radical and hydroxyl radical.