The effect of organic modifiers on the separation of a number of closely related isomeric benzoic acids by capillary electrophoresis is described. It is shown that while a single modifier concentration cannot help resolve the entire electropherogram, organic modifiers do significantly enhance the resolution of parts of the separation system by comparison with 40 mmol l-1 phosphate buffer. The effects on separation and retention times are discussed in terms of the effects on electroosmotic flow and the electrophoretic mobilities of the charged solutes. The effects were found to be modifier specific, although the trends were in the same direction (ie., decreasing electroosmotic flow with increased percentage of organic modifier). The major influence is the manipulation of the electroosmotic mobility.