The recovery of metal ions by electrodeposition from solutions resulting from the lixiviation of spent Zn-MnO2 batteries was studied. It was attempted to optimise the electrodeposition process, the selectivity of ion-separation, the morphologic characteristics, and the anticorrosive and galvanic properties of metallic deposits. The simultaneous deposition of zinc and manganese on different ferrous substrates under various experimental conditions was tested. This allowed us to access the efficiency of the electrodeposition, the morphology and composition of the metallic deposits, as well as their performance as galvanic coating layers. The effect of amine additives, namely, of methylamine and ethylenediamine, on the properties of the coatings was also studied. It was shown that the amines with buffering or passivating effects improve the simultaneous deposition of Mn.