We report on our study of dc voltage-induced structural changes at reduced and oxidized Fe-doped SrTiO3 (Fe:STO) electrode interfaces using second harmonic generation (SHG) together with photoluminescence (PL) method. We show that oxygen vacancy defects play a critical role in determining the local electrical and structural properties of interfacial depletion regions at Schottky junctions. The SHG results show that the dc electric field causes oxygen ions and vacancies to displace toward the anode and cathode in the low field regime, respectively. This process forms electrostrictive distortions within local interfacial depletion regions which are described by Fe:Ti-O bond stretching and bending. Differences in the EFISHG responses from the oxidized and reduced crystal interfaces are explained according to local oxygen vacancy concentrations and dynamics and their effects on the Schottky barrier heights and depletion region widths at each interface. These results are further supported by our PL measurements. Oxygen ion migration toward the Fe:STO surface leads to enhanced fluorescence intensities from in-gap acceptor states. We demonstrate that SHG and PL measurements are well-suited for understanding and resolving the underlying causes of dielectric breakdown processes and device failure brought on by dc electric field and ionic defect migrations in perovskite-type electroceramics.