A series of imprinted silica xerogels that support rhodamine B as the template were synthesized by distinct solgel routes. The adsorption capacity was discussed in terms of isotherm adsorption evaluated in terms of Langmuir, Freundlich, and modified BrunauerEmmettTeller (BET) models. Although only one acid-catalyzed route could be fit with the Langmuir and Freundlich models, yielding a q(m) value of 998.3 mg/g, the BET-modified model showed a good fit for all systems studied. The effect of the solgel route chosen to prepare silica-based sorbent materials that are imprinted to adsorb dyes on their characteristics can be understood by taking into consideration the fact that statistical analysis suggests that other properties (namely, zeta potential, radius of gyration, and percentage of six-membered rings) seem to be relevant to the selective adsorption of dye rather than being indicated by S-BET uniquely. On the basis of the similarity of S-type isotherms observed, we propose that the mechanism of adsorption may be roughly the same for the basic, two-step, nonhydrolytic and the second of two reported acidic routes. This means that, except in the case of the first acid-catalyzed route, there is a tendency for large adsorbed molecules to associate rather than to remain as isolated units.