In the present work, with the goal of finding a viable alternative to Li-ion based electrode system, sodium nickel titanate system (NNT) has been synthesized and its impedance characteristics compared in relation to the established LNMC (LiNi1/3Mn1/3Co1/3O2) electrode system using opto-impedance technique. Thus, obtained opto-impedance results suggest a clear dominant electronic character in the form of charge build-up leading to high capacitance for the former. Also, the significant drop in ohmic resistance observed for the NNT system upon UV irradiation, at elevated temperature (at 55 degrees C) indicates an enhanced thermal safety for the new Na2/3Ni1/3Ti2/3O2 electrode system having potential for electrode applications.