The effect of enhancement factor on the angular dependence of L-l/L-gamma, L-alpha/L-gamma and L-beta/L-gamma X-ray intensity ratios for Sm, Hf, Pb and U elements have been measured by using the 59.54 keV photon energy. The binary systems are prepared as Sm-CeO2, Hf-CeO2, Pb-CeO2 and U-CePO2. The samples have been analyzed in EDXRF system. The measurements are made in scattering angles of 85 degrees, 95 degrees, 105 degrees, 115 degrees and 125 degrees. The L X-ray spectra from different samples were detected by a Si(Li) detector. The results show that the intensity ratios of L X-rays to be greater than expected due to the enhancement effect.