The recovery of Mn and Al from two industrial waste of ferromanganese and aluminum production processes was investigated via implementing a high temperature smelting—aluminothermic reduction process. The experiments were carried out with or without CaO flux addition, and two dross qualities. It was observed that the prepared mixtures of the materials yield homogeneous metal and slag products in terms of chemical composition and the distribution of phases. However, the separation of produced metal phase from the slag at elevated temperatures occurs when a higher amount of CaO is added. Viscosity calculations and equilibrium study indicated that the better metal and slag separation is obtained when the produced slag has lower viscosity and lower liquidus. It was found that the process yields Al-Mn-Si alloys, and it is accompanied with complete recovery of Mn, Si and Fe and the unreacted Al in the process. Moreover, the quality of metal product was less dependent on the slightly different dross quality, and the concentration of minor Ca in metal is slightly increased with significant increase of CaO in the slag phase.