The phase composition, structure parameters, and main magnetic characteristics of BaFe12O19 hexaferrite prepared by the sol–gel combustion method in combination with subsequent annealing at a temperature of 850°С for 6 h are investigated. The properties of the synthesized material are compared with those of the ceramic synthesized by the conventional technology. It is demonstrated that the suggested method is promising for manufacture of ferrite ceramic powders with hexagonal structure.