In this study, we evaluated a novel heterogeneous catalytic system (hemin-ACF/H2O2) based on activated carbon fiber supported hemin for the rapid removal of dyes. Contrast experiments, effects of pH and temperature, and sustained catalytic stability of hemin-ACF for the catalytic decomposition of azo dye RR195 used as a model pollutant were investigated. Surprisingly, the introduction of ACF significantly enhanced the decomposition of dyes by hemin with an obvious improvement in pH tolerance and stability. Inhibition and probe studies combined with electron paramagnetic resonance (EPR) were conducted to ascertain the role of several radicals ((OH)-O-center dot, O-2(center dot-) /HO2 center dot, O-1(2) and Fe-IV=O) on dye degradation. ACF are rich in free electrons, and the pi-conjugated macrocyclic structure of hemin may present convenient channels for the transfer of free electrons from the ACF, promoting the generation of hydroxyl radicals and high-valence iron species. These results are promising because they offer new insight for the application of hemin as a catalyzer upon treatment of organic pollutants and contribute to identification of the interaction between support material and catalyzer from a new perspective. (C) 2013 Elsevier B.V. All rights reserved.