Chemical effects on L X-rays spectra of PrF3, PrCl3, PrBr3, Pr2O3, Pr6O11 and Pr2(SO4)3 compounds have been investigated from measured ILi/ILα (i = l and β6), ILj/ILβ1 (j = η, γ5 and γ1), ILk/ILγ1 (k = γ5 and η) intensity ratios using high resolution poly-chromatic WDXRF, and monochromatic excitation by 6.49 keV in vacuum (10-2 Torr) and Ag Kαβ (22.581 keV) X-rays photons in EDXRF spectrometers. The experimental results clearly exhibit significant variation in measured intensity ratios of L X-ray components of investigated compounds from pure elemental form and theoretically predicted values evaluated using different atomic parameters. Furthermore, the change in inner shell/subshells binding energy resulting from the transitions of outer shell/subshell electrons is also inferred from the shifts of order ∼0.1-0.70 eV in Ll, Lβ2 and Lγ1 components of PrF3, PrCl3, PrBr3, Pr2O3, Pr6O11 and Pr2(SO4)3 WDXRF spectra relative to pure 59Pr. The variation in intensity ratios and shift in Ll, Lβ2 and Lγ1 X-ray components of 59Pr compounds are attributed to crystal defects, structural effects and exchange interactions between core and valence electrons of different ligands attached to central 59Pr atom. The reliable experimental data would be helpful in the theoretical interpretation of standard reference data for inner-shell vacancy decay parameters used in X-ray fluorescence analysis of compound samples.