In the valence transition phenomena, the occupation number of the 4f electrons of the rate-earth atoms will change "continuously" or discontinuously under the condition of different temperatures, different pressures or different compositions (as chemical compounds). Owing to the different occupation number of the 4f electrons, the binding energies of the inner-shell electrons of the rare-earth atoms will vary. We, here, apply a relativistic Dirac-Slater self-consistent field method to calculate the variation of the inner electron binding energies due to valence transition.