A mixture of methyl- and hydroxy-substituted phenols was separated by capillary electrophoresis in pure acetonitrile and propylene carbonate. Interactions between undissociated phenolic compounds and the background electrolytes were investigated. In the present work, benzyltriethylammonium chloride, tetrabutylammonium acetate, and two room temperature-molten salts, 1-butyl-3-methyl imidazolium trifluoroacetate and 1-butyl-3-methyl imidazolium heptafluorobutanoate, were used as background electrolytes. The formation of a negative complex between background electrolyte anion and neutral phenolic compound was observed and the formation constant calculated. The formation constants for anion-analyte complexes were approximately the same in propylene carbonate and in acetonitrile. In both solvents the formation constants were the highest for acetate and the lowest for trifluoroacetate. The separation of analytes was slightly influenced by the nature of the solvent: in acetonitrile the resolution between peaks was higher for 1,3-dihydroxyphenol and 1,3,5-trihydroxyphenol, in propylene carbonate 3-methylphenol and phenol were better separated. It was demonstrated that traces of water influence the mobilities of anion-phenol complexes in propylene carbonate.