New and highly efficient catalyst systems of 5,10,15,20-tetra(4-carboxyphenyl)porphyrinato cobalt salt (TCPPCo(III)X/PTAT, X = CF3COO, OAc, Br, Cl) were developed to catalyze the coupling reaction of carbon dioxide and propylene oxide. It was discovered that the Bronsted acid can accelerate this reaction. A kinetic study demonstrated that the coupling reaction follows the rule of first order reaction and the reaction with addition of organic acid has lower activation energy than that without organic acid. This promotion can be attributed to the additional activation of epoxides by hydrogen bonding. (C) 2012 Elsevier B.V. All rights reserved.