In the present work, the X‐ray intensity ratios, ILk/ILα (k = l, β, γ1,5, γ2,3, γ4), have been measured for different compounds of 66Dy, namely, Dy2O3, Dy2(CO3)3, Dy2(SO4)3.8H2O, DyI2, and the 66Dy metallic foil by tuning the incident photon energies across its Li (i = 1–3) absorption‐edge energies covering the region 7.8–10 keV in order to investigate the influence of chemical effects on these intensity ratios in the presence of the many‐body effects, which become significant at photon energies in proximity to the Li absorption‐edge energies. The present measured intensity ratios ILk/ILα have been compared with two sets of values calculated using the nonrelativistic Hartree–Fock–Slater model‐based Li (i = 1–3) subshell photoionization cross sections, the Dirac–Fock model‐based X‐ray emission rates, and two sets of the fluorescence and Coster–Kronig yields. The L3 absorption‐edge energy of 66Dy in its different compounds and metallic foil has been deduced from the XANES spectra recorded in the present work. The L3 absorption‐edge energy shifts obtained from these absorption‐edge energies are found to increase linearly with the partial charge on the metal atom (66Dy).