Ce intermetallics CeAlNi, CeAlCu and CeNi₂Si₂ have been studied by core-level photoemission spectroscopy to investigate their electronic structure. The Ce 3d XPS data clearly indicate that the final state is a quantum mechanical admixture of 4f⁰, 4f¹ and 4f² configurations in these systems with an increasing 4f⁰ contribution as Cu is replaced by Ni. The two Ni-based systems are found to be mixed-valence systems with n_f<1 while the ground state of the Cu-containing system appears to retain a purely trivalent character with n_f approximately=1. These results are in agreement with the authors earlier reported X-ray absorption and resonant photoemission data. The present study highlights the fact that the replacing of Ni by Cu seems to be propitious for driving the Ce from an intermediate-valence (IV) to a non-IV ground state. The results Ce 3d and Ce 4d XPS are discussed.