L-shell X-ray production cross sections for selected heavy elements (Tl, Pb, Bi), of interest in BIO-PIXE analyses, have been measured by proton and 7 Li ion impact in the energy range 0.8–2.6 MeV and 1.8–3.3 MeV respectively. Further, production cross sections for 7 Li ion impact on Au between 1.0 and 2.4 MeV have been measured. L-subshell ionization cross sections have been extracted and arranged, together with similar results from other laboratories, in an analysis aiming at testing the performance of various theoretical approximations in the description of the ionization process. The disagreement observed at low values of the reduced velocity parameter ξ R L between the data and the predictions of the ECPSSR model is significantly reduced by using a United Atom approximation in the treatment of the binding correction, suggested by our group (ECPSSR-UA). The remaining discrepancies, mostly for the L 1-subshell, are almost completely removed by replacing the screened hydrogenlike wave functions with the more realistic Dirac-Hartree-Slater ones. In the case of 7 Li ions, especially for L 2-subshell, also a more refined Coulomb deflection correction and more sophisticated coupled channel calculations are needed.