Fe-doped Bi12MnO20-BiMn2O5 ceramics was sintered at 1130 K for 6 h in ambient air. Two centro-symmetric phases formed thermodynamically stable self-composite material that was deduced from X-ray pattern analysis. The lattice parameters were a = 10.147(8) -for the cubic I23 Bi12MnO20 phase; and a = 7.545(4) , b = 8.538(1) , c = 5.758(3) -for the orthorhombic Pbam BiMn2O5 phase. The Fe-57 Mossbauer spectrum, recorded at room temperature, has shown pure electronic quadrupolar split. The major doublets reflected the occurrence of Fe3+ ions distributed in two sites, i.e., octahedral Fe4+O6 and square pyramidal Fe3+O5, with preferential occupation of the pyramidal sites, that was consistent with the Pbam phase symmetry. The third doublet resulted from the presence of iron Fe3+ in tetrahedral Fe3+O4 coordination and corresponded to a small admixture of the I23 phase. The DC resistivity rho (DC)(T) dependence on temperature has shown thermally activated features, and the value of E (a,DC) varied in the range of 0.22-0.37 eV. The electric impedance was measured in the f = 20 Hz-1 MHz and 100-690 K range. Two electrical relaxations were determined using the electric modulus formalism MaEuro(3)(T). Low-temperature relaxation has shown the temperature-dependent activation energy E (A,1) = 0.14-0.20 eV and characteristic time values of tau (01) = 10(-10)-10(-12) s in 100-200 K range. It was attributed to the charge transfer between Mn4+/Mn3+ sites. The other relaxation occurred in the 170-220 K range, and it exhibited the following values: tau (02) = 10(-11) s, and E (A,2) = 0.27 eV. A disorder-related VRH polaron model was proposed for rho (DC)(T) and for electric relaxation processes.