This review summarizes our achievements in controlling the chain structures of carbon dioxide-propylene oxide copolymers（PPC）.PPC with number average molecular weight（M

n

） over 2×105 was obtained by double propagation mechanism

the resulted higher M

n

copolymers showed improved thermal and mechanical performance than common copolymers with M

n

lower than 1.5×105.Another way to regulate chain structures was employing crosslinking strategy.PPC bearing small moiety of pendant CC groups was synthesized by terpolymerization of allyl glycidyl ether

propylene oxide and carbon dioxide.Once subjected to UV radiation crosslinking

the dimension stability of the crosslinked copolymer was improved.The third way to regulate chian structures of PPC was controlling its region structure.Lewis base modification strategy on rare earth ternary catalyst was disclosed to enhance nucleophilic ability of active center

PPC with H-T linkages over 83% and M

n

up to 1.0×105

was synthesized at room temperature using Y（CCl

3

OO）

3

-ZnEt

2

-glycerine catalyst and 1

10-Phenanthroline cocatalyst.When H-T linkages increased from 69.7% to 83.2%

a 8℃ increase of T

g

was found

indicating that increase of H-T structure in PPC did raise its T

g

.