This article reports the fabrication (synthesis) and characterizations (structural, microstructural topographic surface, dielectric, transport, impedance, current–voltage, and resistive properties) of a complex lead‐free defect perovskite material of composition LiBiFeMnO5. A preliminary structural investigation of the X‐ray diffraction pattern using N‐TREOR09 methods shows monoclinic symmetry. The scanning electron microscopic spectrum examines the sample's microstructural topographic surface, fractal study, and roughness (using the standard ISO25178). The analysis of Maxwell–Wagner dielectric dispersion, relaxation, and transport mechanisms is investigated utilizing dielectric, impedance, and conductivity spectrum accumulated within the experimental frequency of (1 kHz–1 MHz) at different temperatures (30–500 °C). A nonoverlapping small polaron tunneling conduction mechanism and correlated barrier hopping mechanism in the material have helped to understand its conduction phenomena. The Ohmic and space–charge limited conduction mechanisms are investigated by the slope of the logarithmic electric field (E) and current density (J). The thermistor constant (β) is determined to be 1982.87. The temperature coefficient of resistance is found to be −0.00419, which may be suitable for negative temperature coefficient thermistors, sensors, and other related devices.