A rationally designed meso-tetrakis-(pentafluorophenyl)porphyrin iron(III) chloride [(TF5PP)Fe(III)Cl] was examined as electron reductive dechlorination of environmental harmful 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) in nonaqueous media. Due to the introduction of strong electron-withdrawing groups at meso-positions, (TF5PP)Fe(III)Cl exhibits 100% overall degradation efficiency of DDT by using the controlled potential electrolysis. The time-dependent dechlorination products were analyzed by GC-MS, and the mechanism was studied by in-situ spectroelectrochemical measurements. This rationally designed model catalyst revealed higher degradation speed and efficiency that provide useful information for future rational molecular design towards highly efficient removal of environmental harmful organochloride catalyzed by metalloporphyrins. (C) 2016 Elsevier B.V. All rights reserved.