Ce Lβ emission spectra of CeF 3 and CeO 2 have been measured with energy resolution of ~ 3 eV by a wave-dispersive spectrometer. The observed Ce Lβ 7 band shows certain difference between the two compounds both in profile and intensity. The chemical effects can be reproduced by a band calculation using WIEN2k, which suggests that the Ce Lβ 7 reflects valence-band structure of compounds, and therefore, is hopeful as a probe of selective X-ray absorption fine structure.