Herein we report the structure, thermal and electrical properties of pyrochlore type Pr2-xCaxZr2O7 (x = 0.00, 0.10 and 0.20) compositions. These compounds have been prepared by gel combustion method followed by heating in reducing (Argon/Hydrogen) atmosphere and characterized by powder X-ray diffraction, Raman spectroscopy and ac-impedance studies. The powder XRD and Raman spectroscopic studies revealed the retention of the parent cubic pyrochlore type structure up to the compositions with x = 0.10. The thermal stabilities of the compositions have been investigated by in situ high temperature powder XRD and thermogravimetric studies. A maximum of about 1.25% weight gain due to oxidation of Pr3+ is observed in all the samples. The typical axial thermal expansion coefficients (alpha(a)) for the compositions with x = 0.00, 0.10 and 0.20 are 8.40 x 10(-6), 11.29 x 10(-6) and 11.67 x 10(-6) K-1, respectively. The analyses of impedance and admittance spectra revealed maximum conductivity at x = 0.10, while the activation energy increases with Ca2+ content. At around 770 K, the conductivities of the compositions with x = 0.00, 0.10 and 0.20 are 2.26 x 10(-5) S/cm, 1.88 x 10(-4) S/cm and 1.23 x 10(-4) S/cm, respectively. The activation energy for electronic conductivity for the composition with x = 0.00 and 0.10 are 0.42 and 0.63 eV, respectively. The temperature dependent conductivity of the composition with x = 0.20 composition revealed a deviation around 700 K where the aviation energy decreased from 0.97 eV to 0.38 eV. The electrical properties Pr2-xCaxZr2O7 have been correlated with structural parameters and explained by the coexisting electronic and ionic conductivities. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.