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.