We report x-ray absorption near edge spectroscopy (XANES) of Ca and O K-edges of Ba1-xCaxTiO3 (x = 0, 0.01, 0.08, 1) and understand the spectral features related to the electronic structure of these perovskites. The XANES spectra of Ca K-edge possess a pre-edge peak similar to other 3d transition metals like Ti, Ni when present in perovskite structure and provides information about p-type or hole
doping. Presence of considerable amount of 3d states justifies the reason to consider it as a light 3d transition metal. The O K-edge spectra display characteristic spectral features assigned as eg and t2g and show strong dependence on concentration.