We previously reported that poly(2-methoxyethyl acrylate) (PMEA), which has excellent blood compatibility, contains a large amount of freezing bound water. In order to confirm the role of freezing bound water in determining blood compatibility, poly(tetrahydrofurfuryl acrylate) (PTHFA) was newly synthesized and the thermal properties of water in PTHFA were investigated by differential scanning calorimetry (DSC), as freezing bound water was observed as cold crystallization in DSC heating curves. In addition, the blood compatibility of PTHFA, including activations of platelets, the coagulation system and the complement system, was investigated. The temperature of cold crystallization of water in PTHFA was higher than that of water in PMEA; moreover, the amount of freezing bound water in PTHFA was smaller than that in PMEA. The effect of freezing bound water on blood compatibility was investigated by comparing PTHFA, PMEA, poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2-methoxyethyl methacrylate) (PMEMA). The latter two samples showed no cold crystallization. Activations of platelets, the coagulation system and the complement system were enhanced in the following order: PMEA < PHEMA < PTHFA < PMEMA, PMEA < PMEMA < PTHFA < PHEMA and PMEA < PTHFA < PMEMA < PHEMA, respectively. The above results were reasonably explained by the amount and/or the stability of freezing bound water.