The present study focused on developing a rapid, efficient, and eco-friendly method for the analysis of perfluoroalkyl carboxylic acids (PFCAs) in aqueous matrices. The proposed method was based on esterification of PFCAs by isobutyl chloroformate followed by dispersive liquid–liquid microextraction (DLLME) of the derivatives. Quantitation of the isobutyl esters of PFCAs was carried out by gas chromatography-mass spectrometry with electron ionization. Under the optimal conditions, PFCAs could be determined in linear ranges of 1–1000 ngmL−1 w...