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The various applications of transparent conducting oxides (TCO), e.g., as electrodes in flat panel displays and solar cells or as low-emissivity coatings have stimulated extensive research on their fabrication and properties. Recent experimental and theoretical studies of defect properties have considerably improved the understanding of the limitations of the electrical conductivity of both n- and p-type transparent conductors and of the structural and electronic surface properties of the most important TCO materials. Development of emerging and future applications in the area of transparent thin film electronics with oxide semiconductors as well as the improvement of existing applications require a detailed control of the Fermi level position in the bulk and at surfaces and interfaces of polycrystalline and amorphous TCO materials. This feature article describes how the important parameters for such control can be identified using photoelectron spectroscopy with in situ sample preparation. The parameters influencing doping, work functions, ionization potentials, and surface band bending as well as energy band alignment at interfaces are described and discussed providing a fundamental understanding of important material properties for tailoring TCOs in electronic devices.