In the present work, the Hf target was irradiated by tuning the energy (Ep) of synchrotron radiation across the Li (i = 1–3) edge-energies ranging from 9.6 keV to 14.0 keV in order to measure the cross sections for production of the fluorescent Lk X-rays (k = l, α, η, β1,6, β3, β4, β2,15, β5,7, β9,10, γ1,5, γ2,3,6,8, γ4). These measurements were performed with the aim to check the validity of independent particle approximation (IPA) models at incident photon energies in proximity to the Li absorption edges of a heavy transition element. The measured cross sections were compared with three sets of values calculated using the X-ray emission rates based on the Dirac-Fock model, the Li (i = 1–3) sub-shell photoionization cross-sections based on the non-relativistic Hartree-Fock-Slater model and three sets of the fluorescence (ωi) and Coster-Kronig (fji) yields.