The ring opening copolymerization of trimethylene carbonate (TMC) and dithiolane trimethylene carbonate (DTC) using acidic and basic organocatalysts, i.e., diphenyl phosphate (DPP) and triazabicyclo[4.4.0]elec-5-ene (TBD), was systemically investigated. Interestingly, DPP and TBD gave rise to completely different polymerization kinetics and copolymer sequences. The copolymerization of TMC and DTC using methoxy poly(ethylene glycol) (mPEG OH) as an initiator and DPP as a catalyst proceeded in a first-order manner and to near completion in 72 h for both monomers, yielding well-controlled copolymers with random sequences, predictable molar mass, and low dispersity (M-w/M-n = 1.09-1.19). By contrast, TBD brought about much faster copolymerization of TMC and DTC under similar conditions (high monomer conversion achieved in 2-4 h), to furnish copolymers with controlled molar mass and moderate dispersity (M-w/M-n = 1.27-1.80). Moreover, polymerization kinetics revealed that DTC was preferentially polymerized followed by first-order polymerization of TMC, leading to blocky copolymers. These results signify that type of organocatalysts has a critical influence on polymerization kinetics of cyclic carbonates, copolymer sequence, and molar mass control.