The main objective this communication is to study the structural, morphological, dielectric, and electrical properties of a novel brownmillerite material, KBiMn2O5. Preliminary analysis of the X-ray diffraction (XRD) pattern with N-TREOR09 (trial and error method) with Le-Bail method shows monoclinic symmetry (a = 10.919 Å, b = 5.114 Å, c = 10.453 Å, β = 104.428˚). The examination of scanning electron microscopic spectrum provides the nature of the morphological surface of the sample having an average grain size of 19.89 μm. We have examined Maxwell-Wagner dielectric dispersion, relaxation, and transport mechanisms by analyzing the dielectric, impedance, and conductivity spectra across a wide range of experimental frequencies (1 kHz to 1 MHz) and temperatures (25°C to 500°C). The value of relative permittivity (εr) rapidly increases 200 (room temperature) to 85000 (500°C) with an increase in temperature from room temperature. The high value of εr shows colossal dielectric response (CDR) of the material. The low value of tangent loss (≥ 4.5) can also be applicable to electronic devices. On increasing frequency (1 kHz to 1 MHz), the activation energy of the charged ions from 0.391 eV to 0.328 eV shows a thermally activated relaxation mechanism in the material. The thermistor constant (β), determined as 6317.16, and the temperature coefficient of resistance (TCR) -0.00331 are suitable for high-temperature NTC thermistors, temperature sensors, and other electronic device applications. The study of room temperature non-Ohmic charge conduction and current-voltage charecteristics confirms the suitability of the material for devices.