An aqueous solution containing a fluorine-containing emulsifier in a low concentration of at least 1 ppm by mass and at most 1% by mass (e.g., coagulation waste water after an emulsion polymerization of a fluoropolymer and/or an aqueous solution obtained by washing with an aqueous solution a waste gas from a drying process and/or a heat treating process of the fluoropolymer) is subjected to vacuum concentration under a pressure of at most 100 kPa and a temperature of the aqueous solution of at most 100.degree. C. by means of a heating tube surface evaporation type concentrator equipped with a heat pump or the like, and the fluorine-containing emulsifier is recovered from a highly concentrated aqueous solution containing the fluorine-containing emulsifier in a higher concentration of at least 5% by mass. According to the present method, the fluorine-containing emulsifier can be recovered with a high yield from a low-concentration liquid such as coagulation waste water of a fluoropolymer.