CoFeO/ordered mesoporous carbon (OMC) nanocomposites were synthesized and tested as heterogeneous peroxymonosulfate (PMS) activator for the removal of rhodamine B. Characterization confirmed that CoFeO nanoparticles were tightly bonded to OMC, and the hybrid catalyst possessed high surface area, pore volume, and superparamagnetism. Oxidation experiments demonstrated that CoFeO/OMC nanocomposites displayed favorable catalytic activity in PMS solution and rhodamine B degradation could be well described by pseudo-first-order kinetic model. Sulfate radicals (SO·) were verified as the primary reactive species which was responsible for the decomposition of rhodamine B. The optimum loading ratio of CoFeO and OMC was determined to be 5:1. Under optimum operational condition (catalyst dosage 0.05 g/L, PMS concentration 1.5 mM, pH 7.0, and 25 °C), CoFeO/OMC-activated peroxymonosulfate system could achieve almost complete decolorization of 100 mg/L rhodamine B within 60 min. The enhanced catalytic activity of CoFeO/OMC nanocomposites compared to that of CoFeO nanoparticles could be attributable to the increased adsorption capacity and accelerated redox cycles between Co(III)/Co(II) and Fe(III)/Fe(II).