The electronic structure of La1-x Srx ScO3 single crystal has been studied by x-ray absorption spectroscopy (XAS). The conduction band is mainly composed of Sc 3d state hybridized with O 2p state. The O 1s XAS spectrum exhibits the existence of the Sc 3d -defect-induced state under the Sc 3d conduction band. The intensity of Sc 3d -defect-induced state increases with Sr substitution. The energy separation between the top of the valence band and the bottom of the Sc 3d -induced unoccupied state is in accordance with the energy gap that is expected from optical absorption.