In this present study, nanocrystalline perovskite structure CaMnO3 substituted with Ce and Fe was prepared by a sol–gel technique using citric acid as a chelating agent at 800 °C. The compound was analyzed by powder X-ray diffraction technique and found to be single phased orthorhombic perovskite structure with space group Pnma. The morphology of the synthesized material study is carried out by using SEM and EDX confirmed the chemical compositions of the sample. Electrical measurements were performed to determine the conductive nature of the sample, and the conductivity increases with increasing Fe concentration. Electrode polarization effect was apparently seen in the Nyquist plot and the conductivity measurements. Dielectric relaxations were present in the sample was attributed to the existence of oxygen vacancy, migration in the ions and the Ea is calculated using Arrhenius equation. © 2016, Springer Science+Business Media New York.