Asymmetric, regio- and stereoselective alternating copolymerization of CO2 and racemic aliphatic epoxides proceeds effectively under mild temperature and pressure by using a binary catalyst system of a chiral tetradentate Schiff base cobalt complex [SalenCo(II)X] as the electrophile in conjunction with an ionic organic ammonium salt or a sterically hindered strong organic base as the nucleophile. The substituent groups on the aromatic rings, chiral diamine backbone, and axial X group of the electrophile, as well as the nucleophilicity, leaving ability, and coordination ability of the nucleophile, all significantly affect the catalyst activity, polymer selectivity, enantioselectivity, and stereochemistry. A bulky chiral cyclohexenediimine backbone complex [SalcyCo(III)X] with an axial X group of poor leaving ability as the electrophile, combined with a bulky nuclephile with poor leaving ability and low coordination ability, is an ideal binary catalyst system for the copolymerization of CO2 and a racemic aliphatic epoxide to selectively produce polycarbonates with relatively high enantioselectivity, > 95% head-to-tail connectivity, and > 99% carbonate linkages. A fast copolymerization of CO2 and epoxides was observed when the concentration of the electrophile or/and the nucleophile was increased, and the number of polycarbonate chains was proportional to the concentration of the nucleophile. Electrospray ionization mass spectrometry, in combination with a kinetic study, showed that the copolymerization involved the coordination activation of the monomer by the electrophile and polymer chain growth predominately occurring in the nucleophile. Both the enantiomorphic site effect resulting from the chiral electrophile and the polymer chain end effect mainly from the bulky nucleophile cooperatively control the stereochernistry of the CO2/epoxide copolymerization.