A direct method of surface silyl modification and simultaneous surfactant removal of mesoporous silica is investigated in its physicochemical details. Twelve different silanes of various functionalities are studied. The method employs an alcohol solution of silanes to allow the simultaneous surfactant/silyl exchange process, which results in a more uniform monolayer coverage of the surface and a higher amount of surface attachments of silane. We vary the solution concentration of silanes to study the effect on loadings. It is found that the variation of the surface loading of the silyl group follows a Langmuir adsorption model closely. The method gives one a well-controlled monolayer coverage of the surface. The loadings are determined by the exchange equilibrium. Fittings of the loading data to Langmuir adsorption isotherms give one the adsorption equilibrium constants and maximum surface loadings. We categorize the silanes into three different groups according to the values of the equilibrium constants and discuss them with respect to molecular structures. We also report on the extensive characterizations of the surface-functionalized mesoporous materials, such as nitrogen adsorptions, X-ray diffraction, Si-29 magic-angle spinning NMR, C-13 magic-angle spinning NMR, and IR spectroscopy. The method provides one with a convenient and highly controllable approach to the surface functionalization of mesoporous silica.