New macromonomers based on poly(trimethylene carbonate) (PTMC) were designed and synthesized under precisely controlled conditions using conventional ring-opening polymerization (ROP) techniques. We found that PTMC was connected via the hydroxyl group of N-hydroxyethyl acrylamide (HEAA) or 2-hydroxyethyl acrylate (HEA). However, the preparation of the macromonomers was strongly affected by the concentration of the organic catalyst, inducing unfavorable side reactions. Optimized ROP could be performed by adjusting the concentration of the organic catalyst, 1,8-diazabicyclo[5.4.0]undec-7-ene. The polymerization degree of HEAA-PTMC and HEA-PTMC was maintained in the range of 10 to 50. The reaction was confirmed from the results of 1 H NMR. In this study, we focused on HEAA-PTMC macromonomers. We synthesized the amphiphilic graft copolymer using HEAA and optimal synthetic conditions were proposed.