The significance of theoretical, experimental, and analytical methods in calculating the intensity ratios of L-shell transitions for diverse elements lies in their widespread applications across various domains, including physical chemistry and medical research. In the present paper, empirical values for intensity ratios were computed through polynomial interpolations using experimental databases within the scope of atomic number 39 ≤ Z ≤ 92 for I L β I L α and I L γ I L α , and extending to the range of 39 ≤ Z ≤ 94 for I Ll I L α . Additionally, new theoretical calculations were conducted using the Multiconfiguration Dirac–Fock Method for specific elements. The obtained results were compared with standard theoretical, experimental, and empirical values, showing a reasonable agreement with them.