The La1-xBaxCrO3 (x = 0-0.2) negative temperature coefficient (NTC) ceramics have been prepared by the traditional solid-state reaction method at 1600 A degrees C. Scanning electron microscope images show that the doping of Ba2+ contributes to the increase in the density. X-ray diffraction analysis has revealed that the sintered ceramics crystallize in a single perovskite structure. X-ray photoelectron spectroscopy analysis confirm the existence of Cr3+ and Cr6+ ions on lattice sites, which result in hopping conduction. The presence of the Cr3+ and Cr6+ ions is one of the significant factors that affect the electrical conductivity of La1-xBaxCrO3 ceramics. The resistance of NTC thermistors decreases with the increase of Ba content as a result of the enhancement of Cr6+ Concentration. The obtained values of rho (-50), B (-50/-25) and E (a) are in the range of 49.278-1.9839 x 10(5) Omega cm, 1767.4-3496.9 K, 0.1523-0.3013 eV, respectively.