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The complexation equilibria of cadmium ion(M) with Xylenol Orange(H6L) were studied by potentiometry with a cadmium ion selective electrode. The stability constants for MH3L, MH2L, MHL, ML, M2HL and M2L were obtained. These constants were consistent with the results of potentiometry with only a glass electrode and with those of spectrophotometry. The structure of each species is discussed.