AbstractDispersive liquid–liquid microextraction (DLLME) combined with gas chromatography and mass spectrometry (GC‐MS) was applied to the determination of six organophosphorous pesticides (OPPs) in water samples. The analytes included in this study were prophos, diazinon, chlorpyrifos methyl, methyl parathion, fenchlorphos and chlorpyrifos. Several extraction and dispersion solvents were tested for dispersive liquid–liquid microextraction of these analytes and the best results were obtained using chloroform as extraction solvent and 2‐propanol as dispersion solvent. Calibration curves of the analytes in water samples were constructed in the concentration range from 100 to 1100 ng/L for prophos, diazinon and methyl parathion and in the range from 100 to 1000 ng/L for chlorpyrifos methyl, fenchlorphos and chlorpyrifos. Limits of detection (LODs) were in the range of 1.5–9.1 ng/L and limits of quantification (LOQs) were in the range of 5.1–30.3 ng/L, below the maximum admissible level for drinking water. Relative standard deviations (RSDs) were between 6.5 and 10.1% in the concentration range of 100–1000 ng/L. The relative recoveries (%RRs) of tap, well and irrigation water samples fortified at 800 ng/L were in the range of 46.1–129.4%, with a larger matrix effect being detected in tap water.