A systematic investigation has been carried out on the influence of the acid leaching process parameters on the simultaneous metal recovery (Zn and Mn) from the electrode paste of spent alkaline Zn–MnO2 and spent Zn–C batteries. By introducing a reducing agent namely 30% H2O2 in the H2SO4 leaching solution the extraction efficiency for Mn was increased from 43.5% (no addition of H2O2) up to 97.54% (50% excess H2O2 in comparison with the required stoichiometric amount of H2O2). This H2O2 addition proved to have no influence on Zn extraction efficiency which kept constant at a high level (∼98.4%). A less important influence has been noticed for the molar concentration of H2SO4 in the leaching solution. In the range 0.5 M up to 2 M molar concentration of H2SO4 the extraction efficiency was increased from 78.2% up to 98.4% for Zn and from 63.1% up to 97.2% for Mn. Leaching time up to 60 min proved to gradually increase the extraction efficiency up to 96% for Mn and 98% for Zn but further time increase has no more influence. An attempt has been made to recover the carbon from the leaching residue but its structural characterization is still required.