Chromium(III) derivatives of the tetradentate phenoxyamine ligand H 2 salan, where salan = the N,N 0 -dimethylated bis(aminophenoxide) ligand or the saturated version of the corresponding salen ligand, in the presence of 1 equiv of [PPN]N 3 (PPN=Ph 3 PdN þ dPPh 3 ) are shown to effectively catalyze the copolymerization of cyclohexene oxide and carbon dioxide. X-ray crystallographic analysis reveals the structure of the complex to be different from that of its salen analogue, with an all cis arrangement of the nitrogen and oxygen atoms. Although these catalysts are selective for copolymerizing propylene oxide and CO 2 at ambient temperature with a high degree of regioselectivity, the copolymerization of cyclohexene oxide and CO 2 requires higher temperatures (e.g., 60°C). Nevertheless, the random polymerization of cyclohexene oxide and propylene oxide with CO 2 at ambient temperature provides a terpolymer with a nearly statistical distribution of monomer units. In addition, these catalysts have been shown to be efficient at producing diblock copolymers of poly(propylene carbonate) and poly(cyclohexylene carbonate) as well as triblock copolymers of poly(propylene carbonate)/ poly(cyclohexylene carbonate)/poly(vinylcyclohexylene carbonate).