We have previously reported the hydration structure of a poly(2-methoxyethyl acrylate) (PMEA) antithrombogenic material. In the present study, the hydration structure of a 2-methoxyethyl acetate (MEAc) model monomer for PMEA was explored by means of attenuated total reflection infrared (ATR-IR) spectroscopy and differential scanning calorimetry (DSC). Water in MEAc does not show an evidence for cold crystallization by DSC, while it was found by ATR-IR spectroscopy that MEAc has a hydration structure similar to that of PMEA at a functional group level. Three different types of hydrated water, tightly bound water, loosely bound water and scarcely bound water, were identified in MEAc, as well as PMEA. It was suggested from the present study that the localized and concentrated water cluster having the three types of hydration structure on the surface of PMEA plays an important role in the biocompatibility.