Photoexcited F Kα satellite spectra of CaF2 were studied as a function of excitation energy from threshold. The observed spectra show that the intensity evolution of the KL satellite line is not a monotonic function increasing with excitation energy, in contrast to the prediction from the conventional shake model, but has a small bump. Comparison with the Hartree–Fock calculations indicates that the origin of the bump can be ascribed to resonances of multi‐electron excitation processes in photoabsorption. Copyright © 2003 John Wiley & Sons, Ltd.