Poly(N-vinyl pyrrolidone) (PVP)-based hydrogels with titania nanoparticles (TN) were synthesized by the sol-gel method for the first time and were characterized in different states (native, freeze-dried, air-dried to constant weight and ground to powder, or swollen to constant weight in H2O or D2O) by various methods such as wide-angle and small-angle X-ray and neutron scattering, neutron spin-echo (NSE) spectroscopy, and scanning electron microscopy. The static (static polymer-polymer correlation length (mesh size), associates of cross-links and PVP microchains) and dynamic (polymer chain relaxation rate, hydrodynamic polymer-polymer correlation length) structural elements were determined. The incorporation of titania nanoparticles into PVP hydrogel slightly increases the size of structural inhomogeneities (an increase in the static and dynamic polymer-polymer correlation length, the formation of associates of cross-links and PVP chains). Titania nanoparticles have an impact on the microstructure of the composite hydrogel and form associates with sizes from 0.5 to 2 µm attached to PVP hydrogel pore walls. The PVP and TN/PVP hydrogels show a high degree of water swelling. Moreover, the presence of titania nanoparticles in TN/PVP increases the number of water adsorption cycles compared to PVP hydrogel. The high swelling degree, bacteria-resistant and antimicrobial properties against Staphylococcus aureus allow considering NT/PVP hydrogels for medical applications as wound coatings.