Surface-sensitive photoelectron measurements reveal bulk-to-surface shifts of the Sm 4f/sup 6/ level which imply inhomogeneous valence mixing on the surface of Sm and SmB/sub 6/. The surface valence fraction is estimated to be the same for both materials. The measurements take advantage of a large resonant enhancement of 4f electron emission due to 4d ..-->.. 4f photon absorption, and detailed spectra showing this phenomena are presented. It is shown that the 4d hole in the 4d ..-->.. 4f absorption process stabilizes the 4f state by approx. 4 --7 eV. Exposure of Sm films to oxygen is found to eliminate, rather than increase, the emission from the surface 4f/sup 6/ state, showing that the 4f/sup 6/ state does not arise from oxygen contamination. Observed variations in Sm film spectra are described, including the finding in some films of an unexplained photoemission peak 2.4 eV below the Fermi level. SmB/sub 6/ also displays a broad band of Auger emission when a boron 1s core hole is created, and this is ascribed to electrons in the boron 2p bonding band. Various trends in 4d and 4f binding energies for Sm and SmB/sub 6/ are pointed out and discussed.