We present an analysis of the extensive photolysis of an adsorbate resulting from adsorbate core-level excitation. The system studied was SiF4 adsorbed on Ge(100) at 30 K. Photolysis fragments and molecular species (identified with Si 2p soft x-ray photoemission spectroscopy) were measured as a function of monochromatic (140-eV) photon exposure and adsorbate coverage. The photolysis cross sections for 55-140-eV photons were determined and the neutral photon-stimulated desorption cross section for a selected SiF4 excitation is also presented. In the Si 2p absorption region, it was found that the photolysis cross section was one to three times the preedge value and comparable in magnitude to that of gas phase photoabsorption, while the total yield increased at most by a factor of 1.4. Both of these observations indicate that direct core excitation of the adsorbate is a major path by which photolysis occurs as opposed to an indirect, substrate-driven one.