Combining electron and energy transfer processes is very significant for efficient photocatalytic oxidation of organic molecules. The first synthesized MOF, Co2(L)(2,6-NDC)2·xguest (FJI-Y10, L = bis(N-pyridyl) tetrachloroperylene peryleneimide, 2,6-NDC = 2,6-naphthalenedicarboxylic acid, FJI = Fujian Institute), shows a 2-fold interpenetrated pcu net, in which the 2,6-NDC ligand connects typical Co2(COO)4 paddle wheel clusters to form square lattices pillared by new PDI-type ligand L. FJI-Y10 as a heterogeneous and recyclable photocatalyst is applied for photo-oxidation of benzylamine and its derivatives with an excellent yield of 100%, which is much higher than that (59%) of the equivalent L ligand as a homogeneous photocatalyst under the same reaction conditions. Such a high-efficiency photocatalytic activity attributes to the combination of charge and energy transfer processes in catalyst FJI-Y10 during the catalytic process.