The aim of this paper is the recovery of manganese and zinc from a mixture of zinc–carbon and alkaline spent batteries, containing 40.9% of Mn and 30.1% of Zn, after preliminary physical treatment followed by removal of mercury. Separation of the metals has been carried out on the basis of their different boiling points, being 357°C and 906°C the boiling point of mercury and zinc and 1564°C the melting point of Mn2O3. Characterization by chemical analysis, TGA/DTA and X-ray powder diffraction of the mixture has been carried out after comminution sieving and shaking table treatment to remove the anodic collectors and most of chlorides contained in the mixture. The mixture has been roasted at various temperatures and resident times in a flow of air to set the best conditions to remove mercury that were 400°C and 10min. After that, the flow of air has been turned into a nitrogen one (inert atmosphere) and the temperatures raised, thus permitting the zinc oxide to be reduced to metallic zinc by the carbon present in the original mixture and recovered after volatilization as a high grade concentrate, while manganese was left in the residue. The recovery and the grade of the two metals, at 1000°C and 30min residence time, were 84% and 100% for zinc and 85% and 63% for manganese, respectively. The recovery of zinc increased to 99% with a grade of 97% at 1200°C and 30min residence time, while the recovery and grade of manganese were 86% and 87%, respectively, at that temperature. Moreover, the chlorinated compounds that could form by the combustion of the plastics contained in the spent batteries, are destroyed at the temperature required by the process.