The rationality of using ash and slag waste from coal-fired TPP to obtain high-quality iron-containing concentrate (FC) is demonstrated. Using the method of wet magnetic separation of ash and slag waste from TPP, FC is extracted with Fe2O3 content of 59.2 %. It has been established that the method of chemical enrichment with ammonium hydrofluoride can increase the Fe2O3 content in FC to 79 %; a by-product of the reaction between FC and NH4F•HF is high-quality amorphous silica (white soot). The effect of process temperature on the composition of the resulting FC has been studied, at that the phase composition of iron oxides remains virtually unchanged. Optimal modes of the process are proposed.