A study of the core-electron X-ray photoelectron (X-p.e.) spectra of the f0 compounds La2O3, LaMO3(M = Fe and Co), CeO2, and BaCeO3 is described. Results on the chelate species [La(tmhd)3] and [Ce(tmhd)4](tmhd = 2,2,6,6-tetramethylheptane-3,5-dionato) are included for comparison. Special precautions have been taken to ensure an optimal degree of surface purity of the samples. Satellite structure has been observed for the 4p, in addition to the 3d and 4d, signals in both the lanthanum(III) and cerium(IV) compounds. These satellites arc discussed in terms of coexcitations of the charge-transfer type, principally O 2p→ metal 4f transitions. In the cerium(IV) oxides the satellites are apparently due to energy-gain (representing ‘ shake-down ’) rather than energy-loss (shake-up) processes.