High-resolution CeL(gamma4) emission spectra of CeF(3), Ce(2)S(3), CeF(4), and CeO(2) have been measured using a multicrystal, multidetector spectrometer. The spectra exhibited substantial differences depending on the chemical environment of the Ce ions. By comparing the observed CeO(2) spectrum with the band calculations, we determined that the observed chemical effects of the main emission line were primarily attributable to the transitions of the Ce5p band; the high-energy tail at around 6.539 keV was assigned to the ligand p-->Ce2s cross transition. Further, a key difference between CeL(gamma4) and EuL(gamma4) is discussed with reference to CeL(1)- and EuL(1)-X-ray absorption fine-structures (XAFS). Possible applications of CeL(gamma4) emissions to material characterization are also suggested.