The present study was envisaged to study the electrocatalytic degradation of Acid Blue 80(AB80) using an electrocatalytic collaborative system (E-Mn²⁺-PDS). The degradation efficiencies of different catalytic systems were compared, and the effect of factors such as Mn²⁺ concentration, PDS concentration, pH value and current density on the degradation efficiency of E-Mn²⁺-PDS collaborative system was explored. In addition, the oxidizing substances, decomposition products of AB80 and its degree of mineralization in the system were investigated, and the mechanism of degradation was elucidated. It was found that the degradation rate of E-Mn²⁺-PDS collaborative system on AB80 reached 99.9% in 45 min. pH was found to significantly affect the E-Mn²⁺-PDS collaborative system. When pH=3, the degradation rate of E-Mn²⁺-PDS reached 99.6%. The oxidizing substances in the E-Mn²⁺-PDS system included SO₄^-×, HO×, and active Mn³⁺. In the E-Mn²⁺-PDS collaborative system, AB80 underwent a series of reactions, which produced 11major decomposition products. Additionally, the mineralization rate of E-Mn²⁺-PDS system was 2.6 times that of the direct electrocatalysis in 6 hours. The degradation mechanism was found to be the production of SO₄^-×by Mn²⁺ and the current from PDS, which subsequently reacted with water to generate HO×,this HO×oxidized the Mn²⁺ to oxidizedactive Mn³⁺ in the current, and the three different oxidizing species degraded the pollutants together.