To develop novel environmental-friendly photo-Fenton catalysts, hercynite (FeAl2O4) was prepared via reaction sintering. The catalytic performance in photo-Fenton and the degradation of hercynite for rhodamine B dye was investigated. The results show that the phase composition in the samples is a high-purity hercynite with Fe2+ and Fe3+ complex valence states. The optimal degradation efficiency and TOC removal efficiency are 90.71% and 76.46%, respectively at pH value of 3.14, FeAl2O4 of 1.0 g/L and H2O2 of 2% (in volume fraction). After four cycles, hercynite still maintains a good stability. The synthesized hercynite as an optical photo-Fenton catalyst can be recycled and reused for times, The synthesized hercynite which has a potential application prospect in dye wastewater treatment.