Perfluoroalkyl carboxylic acids (PFCAs) are a class of persistent organic pollutants (POPs), which posed various hazards to organisms, including reproductive, developmental, neurological, and immunological toxicity. Consequently, developing an analytical method aimed at achieving highly sensitive detection of trace amounts of PFCAs in complex samples is clearly of great significance. Herein, the Fluorine-functionalized covalent organic framework (F-COF) was synthesized at ambient temperature, which has the advantages of high specific surface area (1297.7 m