This work describes the synthesis of chitosan hydrogel/SiO2 and chitin hydrogel/SiO2 hybrid mesoporous materials obtained by the sol-gel method for their use as biosorbents. Their adsorption capabilities against four dyes (Remazol Black B, Erythrosine B, Neutral Red and Gentian Violet) were compared in order to evaluate chitin as a plausible replacement for chitosan considering its efficiency and lower cost. Both chitin and chitosan were used in the form of hydrogels. This allowed full compatibility with the ethanol release from tetraethoxysilane. The hybrid materials were characterized by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), Nitrogen Adsorption Isotherms and 13C solid-state Nuclear Magnetic Resonance. Adsorption experimental data were analyzed using Langmuir, Freundlich and Dubinin-Radushkevich isotherm models along with the evaluation of adsorption energy and standard free energy (ΔG0). The adsorption was observed to be pH dependent. The main mechanism of dye adsorption was found to be a spontaneous charge associated interaction, except for EB adsorption on chitin/SiO2 matrix, which showed to involve a lower energy physical adsorption interaction. Aside from highly charged dyes the chitin containing matrix has similar or higher adsorption capacity than the chitosan one. © 2010 Elsevier B.V.