Polymerizable deep eutectic solvents (DES) are promising starting materials for preparation of eutectogels and hydrogels that can be applied in drug delivery, as strain sensors and various components of soft electronics. However, the understanding of relationship between the molecular structure, physicochemical properties and polymerization behavior of such systems in pure state and in their mixtures with water is not well studied yet. In this work we report the results of both computer simulation and experimental investigations for polymerizable choline chloride/acrylic acid DES and its mixtures with water. Molecular dynamics was applied to reveal the influence of water on the structure of polymerizable DES at the molecular and supramolecular levels. The diffusion coefficients of DES components with different water content were measured using NMR. The course of photoinduced polymerization of DES/water mixtures was traced using FTIR spectroscopy, while the molar mass and hydrodynamic characteristics of obtained polyacrylic acid were studied by means of static and dynamic light scattering. It was found that addition of water leads to a gradual decrease in size of the acrylic acid clusters that exist in pure DES and is accompanied by an increase in orientation mobility and diffusion coefficients of components. The maximal molar mass was obtained for the polymer prepared by polymerization of DES with 5 wt% of water. This can be attributed to the optimal combination of acrylic acid clusters size and increased mobility of components.