Abstract Calcium doped lanthanum cobaltite (La1 − xCaxCoO3) (x = 0, 0.2, 0.4, 0.6, 0.8) with different concentrations has been prepared by modified Pechini type polymerizable method. The X-ray diffraction pattern of the calcium doped samples shows the formation of perovskite material in cubic structure. Scanning electron and transmission electron microscopic analysis shows the porous nature of the prepared material. The appearance of peak at 347.5 eV for calcium confirms its presence in the doped samples. Conductance spectra analysis reveals the frequency independent behavior of the samples and the conductivity is related with the particle size. The sample doped with 0.6% of calcium is found to show high conductivity. The temperature dependent conductivity indicates Arrhenius type behavior.