This study summarizes the basic environmental and technical problems, connected with current strategy of recovery of usable materials from ash and slag waste (ASW) of coal-fired power plants. The directions of complex utilization of ASW have been elaborated. In accordance with X-ray diffraction analysis it was determined that the predominant phase of slag component of ASW is an amorphous silicate glass and almost all aluminum oxide is in the amorphous phase. This is a decisive factor in the solubility of aluminum oxide in alkaline solutions and the synthesis of water-resistant hydroaluminosilicates of the R2O⋅Al2O3⋅(2–4)SiO2⋅nH2O type. Thus, a new direction for the application of the slag component of ASW (in a milled state) might be used as a precursor of geopolymer binders. It has been established that heat treatment increases the compressive strength of the geopolymer binder based on ponded ash as well as on milled slag. Both types of binders show the greatest activity after autoclave treatment. Compared to steamed samples, compressive strength increases by 1.8 times, up to 27 MPa for fly ash based binder and up to 60 MPa for milled slag based binder. The result of dry triboelectrostatic separation of ponded ash containing a high percentage of unburned carbon is the production of beneficiated pozzolanic additive for concrete, characterized by improved granulometric and phase composition. It is the way to use the beneficiated ponded ash in formulations of High-Volume Fly Ash Concrete. Besides, the results obtained indicate that the part of ponded ash remained after the beneficiation process contains a high percent of unburned carbon and has a high capacity to adsorb and remove various pollutants from water, in particular phosphates.