This paper presents the research results of the copolymer structure and properties of 2-hydroxyethylmethacrylate (HEMA) with polyvinylpyrrolidone (PVP) and their hydrogels, obtained by block polymerization in the presence of iron sulfate (II). By the methods of chemical analysis, IR spectroscopy, Thermogravimetric (TG) and Differential Thermal Analysis (DTA), the course of grafted copolymerization of HEMA on PVP with the formation of a cross-linked copolymer was confirmed. The results received by scanning electron microscopy showed that due to the copolymerization of HEMA with PVP, macroporous hydrogels with a pore size of 10–30 μm were obtained. The peculiarities of the structure formation of the obtained copolymers depending on the initial composition formulation were established and their structural parameters were investigated: PVP grafting efficiency, PVP content in copolymer, molecular weight of internodal fragment of polymer network, crosslinking degree, and crosslinking density. The interrelation of sorption–diffusion, physical–mechanical and thermophysical properties along with the structure of the obtained materials was proved. It was shown that with the increasing PVP content in the original composition, the efficiency of its grafting and crosslinking density of the polymer network decreased, but the surface hardness, heat resistance, sorption capacity of copolymers in the dry state, as well as ion permeability and elasticity in the swollen state increased, while their tensile strength deteriorated. It is proved that by changing the original composition formulation it is possible to change the structure and hence the properties of the copolymers in the desired direction.