The electrical conductivities of La2-xCaxZr2O7-delta (0 <= x <= 0.07) have been studied in air, and both moist and dry reducing atmosphere (5% H-2 in Ar) in the temperature range between 550 degrees C and 850 degrees C. The powders are prepared by combustion synthesis technique. The electrical conduction mechanism of the sintered samples in various atmospheres is explained with respect to activation energy and defect sites formed within these materials. The sintered materials of all the compositions follow the linear behaviour in the Arrhenius plot. Maximum electrical conductivity obtained at 850 degrees C is 0.013 S/cm for La1.95Ca0.05Zr2O7-delta under moist reducing atmosphere and 0.0093 S/cm for La1.93Ca0.07Zr2O7-delta in air atmosphere. (C) 2013 Elsevier Ltd. All rights reserved.