A headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) automatic method for simultaneous determination of trace amounts of phenol, methylphenols (MPs), chlorophenols (CPs) and bisphenol-A (BPA) in water samples and industrial effluents has been developed. Prior to SPME extraction, a direct derivatisation step using acetic anhydride was performed. Four different SPME fibre coatings (75 mm CAR-PDMS, 65 mm PDMS-DVB, 100 mm PDMS and 85 mm PA) were tested. The parameters affecting the HS-SPME process and derivatisation step studied were: extraction time (560 min) and temperature (40100C), derivatisation time (510 min), sample agitation (0500 rpm), addition of sodium chloride (040%). The GC-MS quantification was performed by internal standard calibration and the limits of detection (LODs) were in the low ng L1. The proposed analytical procedure provided a good linearity (r240.9931) for standard solutions and a repeatability ranging from 4.8 to 15.2% (n¼5). The obtained results show that the developed method was rapid, simple and efficient for phenol, MPs, CPs and BPA analysis, and provides a good alternative to SPE and LLE. Finally, the proposed method has been applied successfully to analyse water samples, municipal solid waste landfill and industrial effluents.