A new sorptive extraction technique, fabric phase sorptive extraction (FPSE), using different coating chemistries: non-polar sol–gel poly(dimethyldiphenylsiloxane) (PDMDPS), medium polar sol–gel poly(tetrahydrofuran) (PTHF), and polar sol–gel poly(ethylene glycol)–block-poly(propylene glycol)–block-poly(ethylene glycol) (PEG–PPG–PEG triblock) and sol–gel Carbowax 20M were evaluated to extract a group of pharmaceuticals and personal care products (PPCPs) with wide range of polarity from environmental aqueous samples. Different parameters affecting FPSE such as sample pH, stirring speed, addition of salt, extraction time, sample volume, elution solvent and desorption time were optimized for each sorbent coated FPSE media. Under optimum conditions, FPSE media coated with sol–gel Carbowax 20M provided the highest absolute recoveries (77–85%) for majority of the analytes with the exception of the most polar ones. Nevertheless, all four sorbents offered better recovery compared to the commercially available coating for stir-bar sorptive extraction based on Ethylene Glycol/Silicone (EG/Silicone). The method based on FPSE with sol–gel Carbowax 20M media and liquid chromatography–(electrospray ionization) tandem mass spectrometry (LC–(ESI) MS/MS) was developed and validated for environmental water samples. Good apparent recoveries (41–80%), detection limits (1–50ngL−1), repeatability (%RSD<15%, n=5) and reproducibility (%RSD<18%, n=5) were achieved.