Barium Titanate and Ni-based multilayer ceramic capacitors have wide commercial applicability, and interfaces are critical to the overall device behavior as they can help control unwanted leakage currents. Here we make use of photoemission methods to investigate the electrostatic barriers formed at BaTiO3/Ni(O) interfaces to understand the implications for electron injection. We find the interface Fermi level in BaTiO3 to evolve smoothly during Ni deposition with a Schottky barrier height for electrons of 0.68 eV, whereas with NiO the Fermi level evolves rapidly with an electron injection barrier of 1.49 eV. In-situ poling shows the Schottky barrier at the BaTiO3/Ni interface is not significantly altered by ferroelectric polarization, consistent with the good screening of the Ni electrode. This study presents a direct quantitative measurement of the interface barrier heights and highlights the significance of the oxidation state of the electrode.