Soil contaminated by combinations of heavy metals and organic pollutants has become an increasingly prominent environmental issue. Developing efficient technologies to synchronously decontaminate such co-contaminated sites is challenging and imperative. In our previous study for the treatment of Copper (Cu) and pyrene contaminated soil, electrokinetics (EK) coupled acidic permanganate (PM) performed best for degradation of pyrene near the injection spot, but it unfortunately prevented the migration of Cu. In order to further enhance the removal efficiency of these contaminants, in this study, batch experiments were conducted to investigate the feasibility of delivering PM by EK under regular refreshment of acidoxidant along with amplification of voltage gradient. The results showed that PM can be transported from cathode to anode to S2 section (near the anode) with a slow mass transfer rate via electromigration and reversed electroosmotic flow, and further delivery was achieved when Cu and pyrene were coexisted. The reaction of pyrene with PM produced a lower soil pH condition, which was conductive to the transport of Cu, and the existence of Cu promoted the migration of PM. The coexistence of Cu and pyrene favored the removal efficiency of the pollutants, and 92.8% of Cu and 70.7% of pyrene were removed after 15 d EK treatment. Thus, EK + acidic PM with regularly supplement of oxidant is appropriate to achieve complete mass depletion of heavy metals and PAHs, especially in low buffered soils.