Two natural polymers, i.e., cellulose and water soluble pullulan, have been selectively oxidized employing the TEMPO-mediated protocol, to allow the introduction of C6-OOH groups. Thereafter, the composite hydrogels of poly(vinyl alcohol) (PVA) and different content of the oxidized polysaccharides were prepared by the freezing/thawing method. The Fourier transform infrared spectroscopy (FTIR) has been used to discuss the degree of interaction between the hydrogels constituents into the physical network. The homogeneity of the prepared hydrogels as revealed by the SEM show an excellent distribution of the oxidized polysaccharides inside the PVA matrix. The samples exhibit self-healing features, since they quickly recover the initial structure after being subjected to a large deformation. The cell viability was performed for the selected hydrogels, all of them showing promising results. The samples are able to load L-arginine both by physical phenomena, such as diffusion, and also by chemical phenomena, when imine-type bonds are likely to be formed. The synergism between the two constituents, PVA and oxidized polysaccharides, into the physical network, propose these hydrogels for many other biomedical applications.