The conversion efficiency of thin-film silicon solar cells needs to be improved to be competitive with respect to other technologies. For a more efficient use of light across the solar spectrum, multi-junction architectures are being considered. Light-management considerations are also crucial in order to maximize light absorption in the active regions with a minimum of parasitic optical losses in the supportive layers. Intrinsic and doped silicon oxide alloys can be advantageously applied within thin-film Si solar cells for these purposes. Intrinsic a-SiOx:H films have been fabricated and characterized as a promising wide gap absorber for application in triple-junction solar cells. Single-junction test devices with open circuit voltage up to 950 mV and ~1 V have been demonstrated, in case of rough and flat front electrodes, respectively. Doped silicon oxide alloys with mixed-phase structure have been developed, characterized by considerably lower absorption and refractive index with respect to standard Si-based films, accompanied by electrical conductivity above 10−5 S/cm. These layers have been successfully applied both into single-junction and micromorph tandem solar cells as superior doped layers with additional functionalities.