AC impedance spectroscopy technique has been used to study electrical properties of Bi3.25La0.75Ti3O12 (BLT) ceramic. Complex impedance plots were fitted with three depressed semicircles, which are attributed to crystalline layer, plate boundary and grain boundary and all three were found to comprise of universal capacitance nature [C = C0wn−1]. Grain boundary resistance and capacitance evaluated from complex impedance plots have larger values than that of plate boundary and crystalline layer. The activation energies (Ea) for DC-conductance in grain boundary, plate boundary and crystalline layer are 0.68 eV, 0.89 eV and 0.89 eV, respectively. Relaxation activation energies calculated from impedance plots showed similar values, 0.81 eV and 0.80 eV for crystalline layer and plate boundary, respectively. These activation energy values are found to be consistent with the Ea value of oxygen vacancies in perovskite materials. A mechanism is offered to explain the generation of oxygen vacancies in BLT ceramic and its role in temperature dependence of DC-conductance study.