Preparative capillary isotachophoresis (ITP) operating in a discontinuous fractionation mode was studied as a sample pretreatment technique for capillary zone electrophoresis (CZE) trace analysis of a group of ten nitrophenols. Different separation mechanisms employed by these capillary electrophoresis techniques made possible a group isolation of the studied analytes by ITP while their CZE resolutions based on differences in the interactions with polyvinylpyrrolidone (PVP) provided suitable conditions for a final analytical evaluation. Experiments with model and practical water samples revealed high and reproducible recovery rates of the ITP pretreatment of nitrophenols when sample loadability limits of the preparative ITP equipment were met. A main disadvantage of the studied ITP-CZE combination was an inefficient use of the pretreated sample as only 0.5% of the fraction containing nitrophenols was used in the final CZE step. Despite these limitations associated with the CZE sample injection, the concentration limit of detection (LOD) for nitrophenols in practical water samples could be reduced to 2-8 ppb concentrations (photometric absorbance detector operating at a 254 nm wavelength) when 200 microL sample volumes were taken for the ITP pretreatment. This was accompanied by an efficient sample clean-up as no other trace ionic constituents originating from the samples were detected on CZE.