In this study, a self-assembly of miniaturized pipette-tip-based solid-phase extraction for the simultaneous extraction of nitroaromatic compounds was developed, with electrospun polyacrylonitrile nanofibers used as sorbents. The electrospun polyacrylonitrile nanofibers were characterized by scanning electron microscopy, FTIR analysis and surface area analysis. Good linearities for the four nitroaromatic compounds (2,6-dinitrotoluene, 2-nitrotoluene, 3-nitrotoluene, and 4-nitrotoluene) were obtained in a range of 250-1000 mu g/L with coefficients of determination >0.99. The limits of detection of these analytes were between 21 and 38 mu g/L. The results showed that the pipette-tip-based solid-phase extraction was effective in extracting nitrotoluenes in the pH regime of environmental interest (approximate to 6). The investigation also revealed that the optimum mass of electrospun polyacrylonitrile nanofibers sorbent was 15 mg and 20 aspirating/dispensing cycles gave the maximum recovery of nitrotoluenes with 200 mu L acetonitrile as the best eluting solvent. Moreover, the performance of the present method was studied for the extraction and determination of nitroaromatic compounds in real environmental water samples and good recoveries ranging from 70 to 115% were found, and respective relative standard deviations of <12% were obtained.