Abstract: The potentiometric curves of 25 basic dyes and 19 quaternary ammonium salts ti-trated with orange Ⅳ (10^-3M or 10^-4M) have been recorded. A method for evaluating the potentiometric titration curves was suggested and their superiority sequences were established. it was found that some of the curves may be applied in electrochemical analysis with higher sensitivity, and the structure of basic dyes and quaternary ammo-nium salts exerts an influence on the titration curve. The superiority sequences of the titration curves would give a possible approach to find new electroactive substances for anion-selective electrodes.