The adsorption of di- and tri-methylamine has been studied at 280 and 276°K, respectively, on a range of silica gels and on silica–alumina. Adsorption–desorption isotherms and isothermal calorimetric heats of adsorption were measured. Heats of adsorption for di-methylamine on silica gel varied from 29.0 kcal/mol at θ = 0.05 to 12.0 kcal/mol at monolayer completion, while for silica–alumina the heats fell from 31.4 to 9.0 kcal/mol between these same values of surface coverage. For tri-methylamine on silica gel, heats fell from 21.0, θ = 0.05, to 10.3 kcal/mol, θ = 1.00, while heats of 21.4 and 9.9 kcal/mol, respectively, were found at these same surface coverages on silica–alumina. The values of the heats of adsorption are discussed in terms of interactions in the adsorbed layer which are believed to be influenced by the pore sizes in the adsorbent and by the basicity of the amine molecules.