An eco-friendly and efficient process for extractive and biomimetic catalytic oxidative desulfurization in fuel oil under mild conditions with H2O2 as oxidant, ionic liquids as extractant and Fe(III) porphyrins as catalysts was reported. The catalytic reactivity of different Fe(III) porphyrins had been investigated in ionic liquids, and the catalysts showed good stability and performance in [Bmim]PF6. The possible mechanism seemed that sulfur-containing compound was oxidized to corresponding sulfone with [(Porp)Fe-III-OOH] or/and [(Porp)Fe-III(O)(+)], which generated in ionic liquids phase. The different reaction conditions such as temperature, mole ratio of H2O2 and sulfur compounds were investigated in the catalytic system with Fe(III)(p-CH3TPP)CI (catal. III) and [Bmim]PF6. The system could be recycled 6 times without obvious decrease of desulfurization efficiency. The reaction system was also applied for the desulfurization of a real diesel fuel. (C) 2016 Elsevier B.V. All rights reserved.