Chemical shift in Ll and Lƞ X‐ray emission lines of 48Cd and 50Sn elements in various chemical compounds was determined with high resolution wavelength dispersive X‐ray fluorescence (WDXRF) spectrometer. The positive and negative shifts were measured in 48Cd compounds viz, CdS, CdB4O7, CdCl2, Cd3(PO4)2, CdCO3, CdI2 and CdO with reference to pure Cd foil and 50Sn compounds viz, Sn(CrO4)2, SnO, SnO2, SnCl2, SnF2, SnF4 with reference to pure Sn foil. The measured energy shifts in Ll X‐ray emission lines range from −0.47 to 1.82 eV and Lƞ emission lines range from −2.67 to 1 eV for both compounds. The effective charges (q, q/, q//, and q///) were calculated from four models (Pauling method, Suchet method, Levine method and Batsonav method) and found to be linear dependence with chemical shift. The measured chemical shifts were correlated with effective charge, number of ligands and electronegativity of the central metal atom in the given compounds.