A process for treating mixtures of organic components, including azeotropic mixtures. The process includes a gas- or liquid-phase membrane separation step in conjunction with a dephlegmation step to treat at least a portion of the permeate vapor from the pervaporation step. The process yields a membrane residue stream, a stream enriched in the more volatile component as the overhead stream from the dephlegmator and a condensate stream enriched in the less volatile component as a bottoms stream from the dephlegmator. Any of these may be the principal product of the process.