A simple and sensitive method based on a modified hollow-fiber liquid-phase microextraction followed by gas chromatography-mass spectrometry has been successfully developed for the extraction and simultaneous derivatization of some nitrophenols (NPs) in soil and rain samples. Microwave-assisted solvent extraction was used for the extraction of NPs from the soil, while the rain sample was directly applied to the previously mentioned method. Briefly, in this method, the analytes were extracted from aqueous samples into a thin layer of organic solvent (dodecane + 10% tri-n-octylphosphine oxide) sustained in the pores of a porous hollow fiber. Then, they were back-extracted using a small volume of organic acceptor solution (25 μl; 10 mg/L N-methyl-N-(trimethylsilyl)trifluoroacetamide, as derivatization reagent, in acetonitrile) that was located inside the lumen of the hollow fiber. Under the optimized extraction conditions, enrichment factors of 255 to 280 and limits of detection of 0.1 to 0.2 μg/L (S/N = 3) with dynamic linear ranges of 1-100 μg/L were obtained for the analytes. The accuracy of the approach was tested by the relative recovery experiments on spiked samples, with results ranging from 93 to 113%. The method was shown to be rapid, cost-effective, and potentially interesting for screening purposes.