Pr1-xCaxCrO3 (x = 0.0-0.5) samples were prepared by the sol-gel method. The sintering temperature of the samples can decrease to 1573 K. The crystal structures of Pr1-xCaxCrO3 at room temperature all are of the othorhombic perovskite GdFeO3-type. Compared to the commonly used Lanthanum chromite interconnect material, Pr0.6Ca0.4CrO3 is better in the properties of conductivity. XPS analysis indicates that the chromium ions are in a mixed valence state. The introduction of Ca2+ into the lattice is compensated by the oxidation of Cr3+ to Cr6+. With increasing X, the amount of Cr6+ increases. The presence of Cr6+ is one of the key factors that affect the electrical conductivity of Pr1-xCaxCrO3. (C) 2003 Elsevier B.V. All rights reserved.