The objective of the present study was to develop and validate a rapid, highly sensitive, and reliable extraction method to determine acrylamide in water samples. The method was based on the derivatisation of the acrylamide in the presence of KBr, HBr and saturated Br₂ solution into 2,3-dibromopropionamide and dispersive liquid–liquid microextraction (DLLME) followed by gas chromatography–electron capture detection (GC–ECD) of the analyte. Different parameters that affect the DLLME process such as types and volumes of disperser solvent, ionic strength of aqueous solution and extraction time were investigated and optimised. Under optimal conditions, excellent linearity was obtained between concentration of acrylamide and the response of ECD with correlation of determination (R²) of 0.9999. The precision of the method, which was determined by calculating the relative standard deviations (RSD) of the at least three replicate measurements, was 3.6%. The method presented in this study is sensitive enough for the determination of acrylamide in different water samples with the limit of detection (LOD) value of 1 ng L⁻¹. The mean percentage recoveries exceeded 91% for all of spiking levels in the real water samples. The results obtained from DLLME method are validated by EPA method 8032A.