Zwitterionic methacrylate polymers with either choline phosphate (CP) (poly(MCP)) or phosphorylcholine (PC) (poly(MPC)) side groups were analyzed to characterize the bound hydration water molecules as nonfreezing water (NFW), intermediate water (IW), or free water (FW). This characterization was carried out by differential scanning calorimetry (DSC) of polymer/water systems, and the enthalpy changes of cold crystallization and melting were determined. The electron pair orientation of CP is opposite to that of PC, and the former binds the alkyl terminal groups at the phosphate esters. The numbers of NFW and IW molecules per monomer unit of poly(MCP) with an isopropyl terminal group were estimated to be 10.7 and 11.3 mol/mol, respectively, which were slightly greater than those of the poly(MCP) bearing an ethyl terminal group. More NFW and IW molecules hydrated the phosphobetaine polyzwitterions, poly(MCP) and poly(MPC), compared with carboxybetaine and sulfobetaine polymers. Moreover, the hydration states of polyelectrolytes were compared with the zwitterionic polymers. Finally, we discuss the relationship between the amount of hydration water and bio-inert properties.