Although most of the zinc-containing catalysts show excellent catalytic activity for the coupling reaction of carbon dioxide (CO2) with epoxides, generally, trace amounts of water in the reaction systems could cause a significant decrease of the catalytic activity. In this work, a nanoporous zinc-cobalt double metal cyanide complex (Zn-Co-III DMCC) with high surface area was synthesized via a modified hydrothermal process using tri-block copolymer EO20PO70EO20 (P123) as the template. When cetyltrimethylammonium bromide (CTAB) was used as the co-catalyst, the Zn-Co-III DMCC/CTAB binary catalyst system could effectively catalyze the coupling reaction of CO2 with hydrous propylene oxide (PO), producing propylene carbonate (PC) with nearly 100% productivity and 100% selectivity. This binary catalyst system could also catalyze the coupling reaction of other commercial epoxides and CO2 without using any solvents with nearly 100% productivity and 100% selectivity. With such new catalyst system, hundreds of ppm water in the reaction system will no longer be the matter. (C) 2013 Elsevier B.V. All rights reserved.