Tungsten (W) doped gallium oxide (Ga2O3) (Ga2-2xWxO3, 0.00 <= x <= 0.30, GWO) polycrystalline ceramic compounds were synthesized via conventional, high-temperature solid-state reaction method. The effect of W-doping on the crystal structure and electronic structure of the resulting GWO materials is studied in detail. The GWO compounds were single-phase, crystallized in beta-Ga2O3 for x <= 0.15, at which point the Ga2O3-WO3 composite formation occurs. The average crystallite size increases with increasing W-content; however, the effect is predominant only in the single phase GWO compounds. Corroborating with structural analyses, the X-ray photoelectron spectroscopy (XPS) measurements reveal the chemical state of W ions vary in GWO compounds as a function of W concentration. The mixed chemical valence states of W (W4+ and W6+) were evident in single-phase GWO compounds where the W-concentration is lower. However, Wions exhibit the highest chemical valence state (W6+) for higher x values, which resulted in the Ga2O3-WO3 composite formation. The Ga ions exists in their highest chemical valence state (Ga3+) in all of the GWO compounds. The scientific understanding of the electronic structure of the GWO materials derived as function of W concentration could be useful while considering the W-doped Ga2O3 materials and/or W-Ga2O3 contacts for electronic and optoelectronic device applications. (c) The Author(s) 2019. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org.