Bi(Fe0.5Mn0.5)O3 is an Mn substituted Bismuth ferrite ferroelectric synthesized following mixed oxide process method of solid-state reaction technique after calcined at 800 °C for 8 h. XRD study approves the development of an orthorhombic single-phase new crystal structure. Electrical characterization of the compound is done by an impedance analyzer. The dielectric and impedance study of the material is investigated in a wide span of frequency (102–106 Hz) and temperature (30–500 °C). The parent compound bismuth ferrite has a higher transition temperature (∼830 °C) which markedly decreases to 470 °C on substitution of Mn is substituted at the B site. Impedance study of the compound exhibits non-Debye type relaxation process. With the rising temperature, the relaxation frequency shifts toward the high frequency side. From the plots of complex impedance, negative temperature coefficient of resistance (NTCR) behavior like semiconductor is noticed. The conductivity is mainly contributed by the grain in the material.