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Among these, glycerol-based thermosets have emerged as promising biocompatible materials. Compared with established glycerol-based thermosets, incorporating shorter-chain aliphatic dicarboxylic acids into the glycerol backbone may enhance hydrophilicity and potentially accelerate hydrolytic degradation, while varying the curing conditions enables tailorable properties for biomedical applications requiring temporary structural support. Herein, poly(glycerol glutarate) (GGA) and poly(glycerol adipate) (GAA) were synthesized via solvent- and catalyst-free polycondensation reactions. Variation in curing temperature yielded thermosets with tailorable swelling, degradation, mechanical, and shape-memory properties. The thermosets exhibited hemocompatibility and cytocompatibility, supporting cell growth and proliferation without inducing intracellular oxidative stress. 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