The pervaporation properties of a methylated-silica membrane were studied on binary ethanol/water and ternary ethanol/water/methanol mixtures. The aim was to acquire a better understanding of the pervaporation mechanisms by studying the effects of feed temperature, permeate pressure, and feed composition on molecular transport. Emphasis was placed on the role of competitive adsorption and dragging and blocking effects between the components in the context of the adsorption-diffusion model. The results show the potential of the membrane for the coupled removal of water and methanol from bioethanol. This attractive application for process intensification was suggested for the first time in this paper.