BaBi4Sn4O15, a Sn-modified ceramic sample of layered ferroelectric oxide family, is developed using a high-temperature mixed oxide route after firing for calcination at 810 °C for 6 h in steps of 50 °C starting from 600 °C. An introductory XRD study of the compound displays the development of the new orthorhombic structured single-phase compound at atmospheric conditions. The electrical behaviors of the compound are investigated in a wide temperature span (30–500 °C) and frequencies ranging from 0.1 kHz to 1 MHz using an impedance analyzer. Dielectric behavior informs that the compound has a phase transition from Ferro to Paraelectric at 370 °C, which is well above room temperature. The impact of temperature and frequency on complex immittance parameters (impedance and modulus) is analyzed using an LCR meter in a broad temperature & frequency span. The electrical properties confirm; (a) the existence of semiconductor-like NTCR (negative temperature coefficients of resistance) behavior, (b) the evidence of the electric relaxation process as a function of temperature, (c) the existence of electric relaxation ascribed to the simultaneous contribution of bulk & bulk interfaces to the electrical behavior, and (d) presence of the non-Debye type relaxation phenomena. The frequency-dependent conductivity follows Jonscher’s universal power law.