Bioleaching of spent batteries was often conducted at pulp density of 1.0% or lower. In this work, metallic ions catalytic bioleaching was used for release Zn and Mn from spent ZMBs at 10% of pulp density. The results showed only Cu2+ improved mobilization of Zn and Mn from the spent batteries among tested four metallic ions. When Cu2+ content increased from 0 to 0.8g/L, the maximum release efficiency elevated from 47.7% to 62.5% for Zn and from 30.9% to 62.4% for Mn, respectively. The Cu2+ catalysis boosted bioleaching of resistant hetaerolite through forming a possible intermediate CuMn2O4 which was subject to be attacked by Fe3+ based on a cycle of Fe3+/Fe2+. However, poor growth of cells, formation of KFe3(SO4)2(OH)6 and its possible blockage between cells and energy matters destroyed the cycle of Fe3+/Fe2+, stopping bioleaching of hetaerolite. The chemical reaction controlled model fitted best for describing Cu2+ catalytic bioleaching of spent ZMBs.