The mesoporous melamine-formaldehyde resin was synthesized in the process of polymerization in the presence of fumed silica as an inorganic template. To differentiate the surface properties, the polymer sample was modified by applying 2-methyl-1-butanol. The surface and structural characteristics of obtained sorbents were investigated using various techniques: XPS, SAXS, and sorption from gas phase. The porous structure of initial and modified melamine-formaldehyde resins was determined from nitrogen adsorption/desorption isotherms. To study the polymer activity toward organic substances dissolved in water, the isotherms of sorption of organics from aqueous phase were measured for a wide range of solution concentrations. The liquid sorption data were analyzed to study the effect of polymer structure and surface properties on sorption processes.