Abstract: A process for separating and recovering an organic phase (e.g., fluorocarbons such as chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons and perfluorocarbons) from a feed stream of a mixture of fluorocarbons and hydrogen fluoride, wherein the mixture is characterized as forming at least one azeotrope or azeotrope-like composition involving at least one fluorocarbon and hydrogen fluoride, by passing the fluorocarbon/HF mixture feed stream through the feed side of a semipermeable membrane unit and then further separating a fluorocarbon-depleted hydrogen fluoride permeate stream and a fluorocarbon enriched residual stream exiting the membrane unit by conventional distillation. An essentially pure fluorocarbon phase and hydrogen fluoride phase are recovered from the distillation with the azeotrope or azeotrope-like distillate being recycled to the inlet of the semipermeable membrane unit.