[en] Photoemission spectroscopy has been used to study a number of aspects of the mixed valent state (corresponding to non-integral 4f occupation) in rare earth systems. Deep core photoemission (e.g., from 3d or 4d levels) allows the measurement of the 4f occupancy and surface valence shifts, and, as well, the indirect measurement of the effect of solid state environment on the energy of hybridization between 4f electrons and conduction electrons. 4f-Derived photoemission has been used to study surface valance and chemical shifts and to infer the nature of the mixed valent ground state. A combination of 4f-derived photoemission and add-electron spectroscopy provides a measurement of the rf Coulomb correlation energy, an important parameter in the mixed valent problem. A review of these approaches will be presented, with emphasis on Ce-based systems, whose behavior falls outside the usual description of 4f-unstable systems