Composite heterogeneous catalysts of ferrous and manganese oxalate (FeC2O4/MnC2O4) were prepared via simple chemical co-precipitation. The catalytic performance was evaluated by determining the degradation efficiency of rhodamine B (RhB). Under optimum conditions, 6-1FeMn showed the best catalytic performance, and the degradation efficiency exceeded 95 % within 2 min, which was 1.4 times more than ferrous oxalate. Under a wide pH range (1–8), 6-1FeMn showed high degradation efficiency for RhB with good recyclability and reusability. By characterizing the catalysts before and after the reaction and analyzing the degradation process, a possible mechanism was proposed: Mn2+ and Fe2+ synergistically catalyzed and produced a large number of hydroxyl radicals (·OH) by forming a composite active site for efficient reactivation. Mn3+ accelerated the transfer between Fe2+ and Fe3+. In addition, C2O4
2− reactivated the active site in situ and enhanced the catalytic properties. This study provides new insight into the catalytic degradation of organic dyes using composite heterogeneous Fenton catalysts.