The aim of the work is the recovery by thermal treatment of manganese and zinc from a mixture of zinc–carbon and alkaline spent batteries, due to the different phase change temperatures of the metals. Activated charcoal, as a reductant of the zinc-bearing phases to metallic Zn, was added to the mixture that was heated in different atmospheres (air, nitrogen, carbon dioxide) at different temperatures and residence times. Characterization of the mixture and of the residues of thermal treatment was carried out by chemical analysis, thermogravimetric and differential thermal analysis, scanning electron microscope and X-ray diffraction and allowed to understand the mechanisms of reduction of zinc and to interpret the formation of different compounds during the process. Results show that recovery of 99% of Zn (grade 96%) at 1200 °C and 97% of Zn (grade 99%) at 1000 °C, are achieved in N2 at 30 min residence time. Recovery of Mn at 1200 °C and 30 min residence time was around 90–100% (90% grade). These products are suitable, after refining, for production of new batteries or higher value-added products. The residue of the treatment, enriched in manganese oxide, could be used in the production of iron–manganese alloys.