This article presents the results of research aimed at optimizing the process of recovery of valuable components from ash and slag waste from thermal power plants. In this work, both experimental and theoretical studies were carried out to substantiate the use of magnetic separation methods for ash and slag waste processing. Ash and slag wastes were chosen as an object of research due to the presence of valuable components such as iron, aluminum, etc., in them. The research results showed that the method of magnetic separation, including high-gradient magnetic separation, can be effectively used in ash and slag waste processing. As a result, the topology of a magnetic beneficiation technological scheme has been proposed to obtain high-value-added products such as high-magnetic iron minerals, low-magnetic iron minerals, and aluminosilicate microspheres. By using magnetic separation in a weak magnetic field, magnetic microspheres containing high-magnetic iron minerals associated with intermetallics, ranging in size from 20 to 80 µm, were recovered. In the second stage of magnetic separation (high-gradient magnetic separation), an iron ore product with an iron content of 50% with a recovery of 92.07% could be obtained. By using scanning electron microscopy, it was found that the main part of microspheres, which contain low-magnetic iron minerals and aluminosilicates, with sizes from 2 to 15 microns, was recovered in the magnetic fraction. This paper proposes a new approach to the enrichment of ash and slag materials using magnetic separation, which will increase the efficiency of their processing and make the process environmentally sustainable.