Abstract: The content of manganese in waste secondary battery was determined by potentiometric titration method. The influence of these factors, including sample dissolving method, interference of coexisting elements, amount of sodium pyrophosphate, and acidity of titration on the determination were investigated. It was found that the sample was dissolved in hydrochloric acid and nitric acid, and potentiometric titration was carried out with potassium permanganate solution in neutral sodium pyrophosphate medium. In order to eliminate the interference of cerium, hydrofluoric acid was used to separate rare earth elements from the waste of Ni-MH battery. The proposed method was applied to the analysis of actual waste materials with the mass fraction of manganese of 5.00%-60.00%, giving RSDs of the determined values (n=11) not more than 0.57%, and recovery of standard addition in the range of 99.6%-101%.