Using X-ray powder diffractions, Mossbauer spectroscopy, and magnetic measurements, the effect of complex dopants (Co2+ + Ti4+) and (Bi3+ + Ti4+) on the fine structure and magnetic properties of M-type barium hexaferrite prepared by hydroxide and carbonate precipitations has been studied. The distribution of cations over five nonequivalent positions of barium hexaferrite with magnetoplumbite structure is discussed. It has been shown that doped barium hexaferrite can be used for high-coercitivity data storage media.