© 2019 American Chemical Society. Transient extreme ultraviolet (XUV) spectroscopy probes core level transitions to unoccupied valence and conduction band states. Uncertainty remains as to what degree the core-hole created by the XUV transition modifies the measurement of photoexcited electron and hole energies. Here, the Si L 2,3 edge is measured after photoexcitation of electrons to the δ, L, and σ valleys of Si(100). The measured changes in the XUV transition probability do not energetically agree with the increasing electron photoexcitation energy. The data experimentally confirm that, for the Si L 2,3 edge, the time-dependent electron and hole energies are partially obscured by the core-hole perturbation. A model based on many-body approximations and the Bethe-Salpeter equation is successfully used to predict the core-hole modification of the final transition density of states in terms of both electronic and structural dynamics. The resulting fit time constants match the excited-state electron thermalization time and the intervalley electron-phonon, intravalley electron-phonon, and phonon-phonon scattering times previously measured in silicon. The outlined approach is a more comprehensive framework for interpreting transient XUV absorption spectra in photoexcited semiconductors.