BaBiO3 (BBO) particles were successfully synthesized through solid-state route, to provide better understanding of its transport properties, which is not well studied yet. X-ray diffraction (XRD) measurement confirmed that the particles were crystallized with monoclinic structure in single phase. The Raman spectrum of BBO sample revealed the existence of two different Bi sites (the octahedral BiO6/3 and the triangular pyramidal BiO4/2 cluster). Subsequently, the observation of low resolution and lattice scale imaging through high resolution transmission electron microscope (HRTEM) indicated the formation of monoclinic BBO particles of size ~ 50-60 nm. The ring pattern obtained from selected area electron diffraction (SAED) inveterate polycrystalline nature of the sample and calculated structural parameters well harmonized with XRD results. As expected, BBO showed semiconducting behavior with resistivity of ~ 3.8 kΩ-cm at room temperature along with an excellent NTC (negative temperature coefficient) thermistor characteristic. The dielectric measurements and impedance spectroscopy studies reveal that BBO exhibit two typical characteristics, i.e., diffuse phase transition and frequency dependent dielectric maxima, of relaxor oxides; with negative dielectric constant above 550 K.