An example of crystalline CO

2

-based polymer from the asymmetric alternating copolymerization of CO

2

and cyclohexene oxide is reported. Isotacticity of poly(cyclohexene carbonate) (PCHC) has the critical influence on the crystallinity

and only copolymers with a isotacticity of more than 90% are crystallizable. The stereoregular PCHC is a typical semi-crystalline thermoplastic

and possesses a high melting point (

T

m

) of 215-230℃ and a decomposition temperature of

ca.

310℃. The spherulitic morphology of (

R

)-PCHC grows in a clockwise spiral from a center

and that of (

S

)-PCHC is a counterclockwise spiral

while the stereocomplex of (

S

)-PCHC/(

R

)-PCHC (1/1 mass ratio) presents lath-like dendritic crystal. The novel crystalline CO

2

-based polycarbonate represents a rare example of optically active polymers with unique crystallization behavior. Our findings reflect the critical influence of stereoregularity on the crystallization for this kind of polymeric materials

and may lead to developments of thermal-resistance CO

2

copolymers for application in engineering thermoplastics.