Micellar electrokinetic capillary chromatography(MECC) and HPLC with ion-pairing mechanism were applied for the separation of the well known environmental wastes from dye industry. These compounds include H-acid, J-acid, gamma-acid, orthanilic acid, sulfanilic acid and 2-naphthylamine-1,5-disulfonic acid, and are known to be the diazo components of the azo dye. MECC method was also applied to separate few acid dyes including Acid Orange 7, Acid Orange 5 and Acid Blue 92 and direct dye such as Direct Red 80. Informations about the diazo components of any azo dye could be obtained by comparison of electropherogram of the reduction solution of a given dye with those obtained from standard materials such as H-acid, J-acid, gamma-acid, orthanilic acid, sulfanilic acid and 2-naphthylamine-1,5-disulfonic acid. It has been concluded that MECC and HPLC with ion-pairing mechanism could be successfully applied for the analysis of unknown dyes and their diazo components.