The preparation of M- and W-type Ba-hexaferrite particles by the glass crystallization method was investigated. For this purpose that part of the pseudoternary phase diagram Fe2O3-BaO-B2O3was elaborated in which primary crystallization of BaFe12O19occurs. This three-dimensional region was found to be located within the triangle Fe2O3-BaB2O4-BaFeO2,5. The lowest temperature of primary crystallization of BaFe12O19is close to 800°C near the composition 55 mol% BaO, 20 mol% B2O3and 25 mol% Fe2O3. Using the knowledge of that system it was also possible to synthesize W-type Ba-hexaferrite particles (BaZn2Fe16O27) by the glass crystallization method. Magnetic data of M- and W-type hexaferrite pigments prepared by that method are given. Particle size from a tenth of a micron to more than ten microns was obtained.