A lipophilic and electron-rich metallophthalocyanine Mn(III)Cl(alpha,alpha '-n-OC(5)Hu(11))(8)Pc has been synthesized and characterized. A series of electrochemical experiments demonstrate that the Mn(III)Cl(alpha,alpha '-n-OC5HH)(8)Pc complex can be used as a catalyst for highly efficient carbon-chloride bond cleavage of environmental toxic hexachlorocyclohexanes (HCHs) through electrochemical catalysis, and that the increased catalytic efficiency is related to the enantiomeric carbon-chloride sigma-bond of HCHs.