Solidified floating organic drop microextraction (SFODME) in combination with gas chromatography with an electron capture detector was used for separation/enrichment and determination of 2,5-dichloronitrobenzene, 2,3-dichloro-nitrobenzene, and 2,6-dichloro-4-nitroaniline in water samples. The main parameters affecting the performance of SFOME, such as solvent volume, extraction time, stirring rate, extraction temperature, sample volume, nature of the solvent and ionic strength were optimized. Under the optimum experimental conditions, good relative standard deviations of 7.5%, 6.9%, and 9.3% for 7 extractions and determination of 50 ng L −1 of 2,5-dichloro-nitrobenzene, 2,3-dichloro-nitrobenzene and 2,6-dichloro-4-nitroaniline were obtained, respectively. Enrichment factors of 1390, 1398, and 1362 and detection limits of 1.4, 1.2, and 10 ng L −1 for 2,5-dichloro-nitrobenzene, 2,3-dichloro-nitrobenzene, and 2,6-dichloro-4-nitroaniline were found, respectively.