A process is provided for separating a mixture of alkoxysilanes and alkanol, e.g., the crude product effluent of the Direct Reaction of silicon metal with alkanol, which comprises: a) introducing a mixture of alkoxysilane(s) and alkanol to a separation unit possessing a separation membrane having a first surface and an opposing second surface; b) contacting the mixture of alkoxysilane(s) and alkanol with the first surface of the separation membrane whereby one or more components of the mixture selectively absorb into the first surface and permeate therethrough to the second surface under the influence of a concentration gradient across the membrane thereby separating the mixture into an alkanol-enriched permeate fraction and an alkanol-deficient retentate fraction or an alkoxysilane-enriched permeate fraction and an alkoxysilane-deficient retentate fraction; and, c) recovering the permeate fraction.