Effect of the heat treatment of carbonate-hydroxide precipitates on the phase composition, structure and magnetic properties of M-type barium hexaferrite has been investigated using the Mőssbauer spectroscopy, X-ray phase analysis and magnetic measurements. The distribution of Fe3+ ions over structural sites of barium hexaferrite with different degree of ferritizations has been defined. The conditions of single-domain behavior of barium hexaferrite nanoparticles in the magnetic field have been discussed. Obtained results explain the formation of magnetic structure during the synthesis of barium hexaferrite. This information could further be used for optimizing conditions for synthesis of nanosized barium hexaferrite with high-level properties.