Ethanol—water concentration profiles in cellulose acetate membranes were measured under steady-state pervaporation conditions. Knowledge of these profiles leads to a better understanding of the diffusion process during pervaporation. The concentration profiles were determined by a film-stack method, using three to six layers. It is shown that permeation of ethanol—water mixtures proceeds in a coupled way and that crossterm diffusion coefficients need to be considered. Furthermore, the occurrence of sorption resistances at the feed/membrane interface can be established from these experiment