Disclosed are processes for reacting a perfluorinated olefin with an alcohol, an alkali metal hydroxide, and water in the presence of a phase transfer catalyst to form a reaction product mixture that separates into an aqueous phase and an organic phase. Alcohol may be present in an effective amount sufficient to form a third phase comprising at least 50% of the phase transfer catalyst. The third phase can be separated from the organic phase. Also disclosed are methods for recovering and recycling the phase transfer catalyst used in the reaction.