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Transient X-ray and extreme ultraviolet (XUV) spectroscopies have become invaluable tools for studying photoexcited dynamics due to their sensitivity to carrier occupations and local chemical or structural changes. One of the most studied materials using transient XUV spectroscopy is α-Fe2O3because of its rich photoexcited dynamics, including small polaron formation. The interpretation of carrier and polaron effects in α-Fe2O3is currently carried out using a semi-empirical method that is not transferrable to most materials. Here, an ab initio, Bethe-Salpeter equation (BSE) approach is developed that can incorporate photoexcited-state effects into arbitrary material systems. The accuracy of this approach is proven by calculating the XUV absorption spectra for the ground, photoexcited, and polaron states of α-Fe2O3. Furthermore, the theoretical approach allows for the projection of the core-valence excitons and different components of the X-ray transition Hamiltonian onto the band structure, providing new insights into old measurements. From this information, a physical intuition about the origins and nature of the transient XUV spectra can be built. A route to extracting electron and hole energies is even shown possible for highly angular momentum split XUV peaks. This method is easily generalized to K, L, M, and N edges to provide a general approach for analyzing transient X-ray absorption or reflection data.