The presented paper is focused on preparation and subsequent characterization of structural and transport properties of hydrogels with double-network concerning their application potential. Hybrid hydrogels were prepared as a combination of synthetic polymer and natural polysaccharide, such as polyvinyl alcohol (PVA) and sodium alginate (SA), where mass ratio of those polymers was 1:1. In the preparation of the gel’s hybrid network a freeze-thawing cycle technique for physical cross-linking of PVA was used, also calcium ions were used for ionic cross-linking of sodium alginate. Lecithin as a modification of the internal structure of hybrid hydrogels was also used in gel’s system preparation. Physicochemical methods were used to characterise their viscoelastic, swelling and transport properties. Rheology measurements, specifically oscillation and amplitude tests, were used to study these mechanical properties. Morphology of the prepared hybrid hydrogels was confirmed by electron microscope scanning. Transport and release properties of gel systems were determined by diffusion experiments with the UV-VIS spectrometry detection method, in which an organic dye (methylene blue) was used as a model probe.