The interaction of poly(trimethylene carbonate) (PTMC) with hydroxyl group compounds was investigated as a model for polymer blending with polysaccharides. While 1-butanol, 2-butanol, ethylene glycol, and 1,2-cyclohexanediol showed almost no detectable interaction with PTMC in both solution states with the 1H NMR and solid states with the FT-IR, glucose and cellobiose suggested a slight change in the spectral pattern in FT-IR analysis. The thermal properties of the blended samples of PTMC and these hydroxyl groups were also investigated. Although the blends of PTMC with 1-butanol and 2-butanol did not influence thermal degradation behaviors due to their low boiling points, the PTMC blend with a higher number of hydroxyl groups, especially glucose and cellobiose, tended to increase thermal resistance and glass transition temperature, hence showing the existence of an interaction through hydrogen bonding. © 2024 by the authors.