The pervaporation transport of methanol through an amorphous microporous methylated silica membrane was studied experimentally and analyzed through modeling within a Maxwell−Stefan (MS) framework. The experimental conditions cover a temperature range of 60−155 °C and absolute pressures up to 16 bar. Exerting higher absolute pressures on the liquid feed-side of the membrane did not lead to enhanced fluxes, confirming that (i) the selective layer of the 56.8 cm2 membrane was a closed layer and defect-free, and (ii) the chemical potential gradient of the permeating component is an appropriate driving force to describe the transport through the microporous membrane. Both the adsorption isotherm and the heat of adsorption (−ΔHi,ads) were determined, and a two-site Langmuir isotherm adequately correlated the heterogeneous adsorption behavior of methanol in amorphous silica. Different levels of detail were adopted for modeling the diffusion transport through the selective layer, after having accounted for the re...