The effects of radiation damage at the surfaces of CaF2 films grown on Si(111) substrates have been studied and the electronic transitions responsible for the formation of surface F centers have been identified by photon-stimulated desorption and soft x-ray photoelectron spectroscopy. The dominant desorption channel for F+ ions is a direct Auger-stimulated process following an electronic transition from Ca 3p to 3d-derived states above the CaF2 conduction band minimum. At the Si 2p edge, there is an indirect x-ray induced electron-stimulated desorption process that contributes only slightly to die desorption of F+. The changes in the kinetic energy distributions of the desorbing F+ ions as a function of film thickness are also discussed.