Previously, we reported that poly(2-methoxyethylacrylate) (PMEA) showed excellent blood compatibility and implied that the water structure in PMEA contributed to the blood compatibility. In this study, the relationship between the water structure and the blood compatibility is clarified by studying the influence of the monomer composition of poly(MEA-co-HEMA) on the water structure and the blood compatibility of the copolymers. The water in the polymer was classified into three types: free water, freezing bound water, and nonfreezing water. The polymers with 0-30 mol % of HEMA content had a significant amount of freezing bound water, and the amount decreases greatly when the composition of HEMA exceeded 30 mol %. On the other hand. the amount of other water increased simply with an increase of HEMA content. The evaluation of the platelet compatibility of poly(MEA-co-HEMA) revealed that the adhesion number and the morphological change of platelet on the copolymer surface were least when the HEMA content was 0-20 mol %. These two results strongly suggest that the freezing bound water relates to the platelet compatibility of the polymers.