Two naturally occurring polymers, i.e. cellulose and pullulan have been selectively oxidized employing the well-established TEMPO/NaClO/NaBr protocol, in order to introduce carboxylic groups. The C6-oxidized products were used for preparing hydrogels with polyvinyl alcohol (PVA), using various ratios of oxidized polysaccharides/PVA. The resulted hydrogels were thoroughly investigated using spectral and microscopic techniques and their rheological and swelling features were analyzed. These hydrogels were further tested for the incorporation and release of L-arginine. The loading of L-arginine takes place by physical phenomena, such as diffusion, but also by chemical phenomena, when it is possible to form imine-type bonds, especially to materials with oxidized pullulan, which have a prolonged release of the drug to physiological pH. The main advantages when using the oxidized cellulose or pullulan for the hydrogels preparation, are:– water is used as a sole solvent for both components oxidized polysaccharide and PVA, avoiding the use of complicated solvent mixtures required by the unoxidized cellulose,– due to the extremely high number of COOH groups incorporated after oxidation, the oxidized polysaccharide component takes over the role of crosslinking agent, in this case the supplemental presence of a crosslinking agent, being not necessary.