Oxygen deficient perovskites LaTiO 3− δ and La 0.8 A 0.2 TiO 3− δ (A=Ba, Sr, Ca) were synthesized by sol–gel method. The effect of divalent dopants on microstructure is investigated in detail using X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The oxidation states of La 3+ and Ti 3+ ions have been deduced using X-ray Photoelectron Spectroscopy (XPS). Impedance spectroscopy was used to analyze the total conductivity, an increase in conductivity was observed after doping in the A-site with divalent cations Ba, Ca and Sr. Among the investigated perovskites La 0.8 Ca 0.2 TiO 3− δ exhibited the maximum conductivity of 1.22×10 −2 S/cm in air atmosphere at 650°C.