A novel method for the enrichment of nitroaromatic compounds present in water samples is presented here coupling hollow fibre liquid phase microextraction (LPME) with gas chromatography. A hydrophobic porous polypropylene hollow fibre was used as the interface between the donor water sample and microvolumes of the acceptor organic phase. Parameters such as extraction solvent, stirring rate, salt concentration and sampling time were studied and optimised. Overall, extraction of 11 nitroaromatics was achieved by exposing 3μl of toluene for 20min in a 5ml stirred aqueous solution at room temperature. The developed protocol yielded a linear calibration graph in the concentration range 10-500μgl - 1 and the limits of detection were calculated to range between 0.29 and 0.87μgl - 1 . Precision expressed in terms of relative standard deviation varied between 6.1 and 11.8%. The developed hollow fibre LPME method was subsequently used successfully to monitor the sonochemical degradation of an aqueous solution containing 100μgl - 1 of each target analyte at an ultrasonic frequency of 80kHz. Ultrasonic treatment was found capable of efficiently removing the 2-, 3- and 4-nitrotoluene isomers as well as the 2- and 4-amino dinitrotoluene isomers within 300min of irradiation. The rest of the analytes were more recalcitrant and significant removal was not observed even after prolonged times of ultrasonic irradiation.