Rare earth (Nd, Y, La) p-tert-butylcalix[n]arene (n=4, 6, and 8) complexes alone have been developed to catalyze random and block copolymerizations of trimethylene carbonate (TMC) and 2,2-dimethyltrimethylene carbonate (DTC). The random or block structure and thermal behavior of the copolymers have been characterized by SEC, NMR, DSC, XRD and PLM. Random copolymer with M w of 14,100 and M w /M n of 1.36 was prepared by neodymium p-tert-butylcalix[6]arene complex under the conditions: [TMC+DTC] 0 /[Nd]=400, 80°C, 8h. The reactivity ratios of TMC and DTC are measured to be r TMC =4.68 and r DTC =0.163, respectively. Random copolymerization could be well designed by the feeding ratio to prepare copolymers with controlled T m and T g . Only 8% TMC units in the polymer chain destroyed the crystallization of PDTC showing no T m of the copolymer in the DSC analysis.