Polypyrrole(PPy) supported Cr(III)(salen)Cl catalyst was prepared for alternating copolymerization of cyclohexene oxide and carbon dioxide. The supported catalyst and the copolymerization products were characterized by FTIR, XRD, XPS, ICP-MS, SEM, TEM, NMR, gel permeation chromatography, thermogravimetric analysis and differential scanning calorimetry. After the study, we concluded that the homogeneous Cr(III)(salen)Cl is successfully supported on the PPy, and its catalytic performance is much better than the homogeneous one. Moreover, the copolymerization product catalyzed by PPy-Cr(III)(salen)Cl exhibits higher molecular weight, narrower molecular weight distribution, superior thermal stability and selectivity.