Abstract Adsorption isotherms of BTX aromatic hydrocarbons (benzene, toluene, and p-xylene) on pristine (SiO 2) and metal-doped (Ag–SiO 2, Cu–SiO 2 and Fe–SiO 2) mesoporous and microporous substrates were measured and interpreted. These adsorbents were synthesized by the sol–gel procedure and their BTX sorption isotherms were obtained by the gas chromatographic technique (GC) at several temperatures in the range 423–593 K. The uptake amount of these hydrocarbon adsorptives on SiO 2, Ag–SiO 2, Cu–SiO 2 and Fe–SiO 2 mesoporous and microporous substrates was temperature-dependent. Additionally, the interaction of BTX molecules with the pore walls was evaluated by means of the corresponding isosteric heat of adsorption ( q st), which was found to follow the next increasing sequence: q st (benzene) < q st (toluene) < q st ( p-xylene). In general, the isosteric heat of adsorption of aromatic BTX compounds on microporous silica depicted an increasing tendency when the amount adsorbed was raised. This was a consequence of the existence of cohesive interactions (adsorbate–adsorbate) besides of the adhesive ones (adsorbate–adsorbent). The inclusion of silver or iron atoms within the SiO 2 structure leads to an increased adsorbed amount of BTX molecules on the solid surface if compared with the Cu–SiO 2 adsorbent. The adsorption of benzene, but not of toluene and p-xylene, molecules on pristine SiO 2 is facilitated by the pore size of this substrate since this is the highest of all materials.