Fluorotelomer alcohols (FTOHs) are one of the major classes of per- and polyfluoroalkyl substances (PFAS). Due to their potential toxicity, persistence, and ubiquitous presence in the environment, some common PFAS are voluntarily phased out; while FTOHs are used as alternatives to conventional PFAS. FTOHs are precursors of perfluorocarboxylic acids (PFCAs) and therefore they are commonly detected in water matrices, which eventually indicate PFAS contamination in drinking water supplies and thus a potential source of human exposure. Even though studies have been conducted nationwide to evaluate the degree of FTOHs in the water environment, robust monitoring is lacking because of the unavailability of simple and sustainable analytical extraction and detection methods. To fill the gap, we developed and validated a simple, rapid, minimal solvent use, no clean-up, and sensitive method for the determination of FTOHs in water by stir bar sorptive extraction (SBSE) coupled with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Three commonly detected FTOHs (6:2 FTOH, 8:2 FTOH, and 10:2 FTOH) were selected as the model compounds. Factors such as extraction time, stirring speed, solvent composition, salt addition, and pH were investigated to achieve optimal extraction efficiency. This “green chemistry” based extraction provided good sensitivity and precision with low method limits of detection ranging from 2.16 ng/L to 16.7 ng/L and with an extraction recovery ranging 55%–111%. The developed method were tested on tap water, brackish water, and wastewater influent and effluent. 6:2 FTOH and 8:2 FTOH were detected in two wastewater samples at 78.0 and 34.8 ng/L, respectively. This optimized SBSE-TD-GC-MS method will be a valuable alternative to investigate FTOHs in water matrices.