A series of new types of composites (biopolymer-silica materials) are proposed as selective and effective adsorbents. A new procedure for the synthesis of chitosan-nanosilica composites (ChNS) and chitosan-silica gel composites (ChSG) using geometrical modification of silica and mechanosorption of chitosan is applied. The highest adsorption efficiency was achieved at pH = 2, hence the desirability of modifications aimed at stabilizing chitosan in such conditions. The amount of chitosan in the synthesis grew to 1.8 times the adsorption capacity for the nanosilica-supported materials and 1.6 times for the silica gel-based composites. The adsorption kinetics of anionic dyes (acid red AR88) was faster for ChNS than for ChSG, which results from a silica-type effect. The various structural, textural, and physicochemical aspects of the chitosan-silica adsorbents were analyzed via small-angle X-ray scattering, scanning electron microscopy, low-temperature gas (nitrogen) adsorption, and potentiometric titration, as well as their adsorption effectiveness towards selected dyes. This indicates the synergistic effect of the presence of dye-binding groups of the chitosan component, and the developed interfacial surface of the silica component in composites.