Hexagonal ferrites BaxSr1−xFe12O19 (x=0.05, 0.15, 0.25, 0.35) were prepared by sol–gel and conventional solid state reaction techniques. Their magnetic properties, investigated by magnetometry and Mössbauer spectroscopy, were discussed in correlation to structural aspects. Whereas the hexaferrites obtained by sol–gel are almost single phase, the ones prepared by the conventional solid state reaction technique present a low amount of BaFe2O4 as secondary phase. All samples show a relative high coercive field and remanent magnetization, as specific features for permanent magnet behavior. The five Fe3+ sites of the specific elemental cell have been revealed and their relative occupancy has been derived from the Mössbauer spectra. The analyzed samples show a sensitivity of the magnetic properties (magnetic moment and anisotropy) with respect to the occupancy of the different Fe sites.