Three different varieties of mesoporous silicas were synthesized by varying the postsynthesis treatment of an as-synthesized ordered mesoporous material type MCM-41. The resulting materials consisted of a purely siliceous MCM-41, a pore-expanded MCM-41 (PE-MCM-41C), and a surfactant-laden pore-expanded MCM-41 (PE-MCM-41E) and were evaluated as adsorbents for two types of volatile organic compounds, i.e., chlorinated and aromatic hydrocarbons. Values of heat of adsorption and Henry's law constant were determined by pulse chromatography. Additionally, adsorption capacities were calculated with a dynamic method using breakthrough curves for single components in dry and humid environments. The surfactant-containing material exhibited good compatibility with chlorinated compounds in terms of heat of adsorption and efficiency in gaseous streams containing moisture. Purely siliceous mesoporous materials, i.e., MCM-41 and PE-MCM-41C, were more selective toward aromatic hydrocarbons but also gave rise to exceptionally strong adsorption.