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The crystalline stereocomplexed polycarbonates can be prepared by mixing enantiopure polymers with opposite configuration, which derived from the asymmetric copolymerization with CO 2  using enantiopure catalyst or/and chiral epoxides. Herein, we develop a powerful strategy for producing crystalline intramolecular stereocomplexed polycarbonates from  racemic  catalysts, which possess similar thermal stability and crystalline behaviour in comparison with the stereocomplexes by mixing opposite enantiopure polymers. Living polymer chains shuttle between catalyst molecules with different configurations to produce diastereomeric active species which is suggested to be responsible for the formation of isotactic multiblock polycarbonates in  racemic  bimetallic cobalt catalyst-mediated stereoselective copolymerization of CO 2  and  meso -epoxides. Solid-state NMR spectroscopy study suggests that the interaction in the carbonyl and methine regions is responsible for the strong crystallization capacity and compact package structure in the crystalline polycarbonates.

Crystalline CO2-based polycarbonates prepared from racemic catalyst through intramolecularly interlocked assembly