Graft copolymers of polysaccharides with side chains of carbon-chain monomers have significant potential for a variety of practical applications. In this work, the effect of the N,N-methylenebisacrylamide (MBA) introduction stage and acrylamide concentration in microwave-assisted radical copolymerization with xanthan gum on the structure and sorption properties of the cross-linked graft copolymer was studied. It has been found that the spatial network density and average molecular weight of interstitial fragments can be controlled by varying these factors. Moderate crystallinity (<50%) and a highly developed surface of our synthesized samples were revealed using XRD and SEM. The graft copolymer exhibits the Schroeder effect; its liquid water sorption obeys Fick’s law and increases with MBA introduction at later stages and with increasing grafting degree, reaching 17.2 g/g. Studying the methylene blue sorption kinetics using pseudo-first/pseudo-second order models, a combined model and an average pseudo-order model have shown that the lower the monomer concentration in the reaction mixture and the earlier (from the onset of the reaction) the cross-linking agent is introduced, the higher the equilibrium sorption. The observed “equilibrium degree of sorption on xanthan gum vs. pseudo-order” relationship, which passes through a minimum, is explained by chemisorption and the sorbate consumption effect. An assumption is made about the prospects of using our synthesized copolymers for designing selective sorbents and ion-exchange membranes.