The L-shell X-ray production cross sections have been measured for sulphur ions in the energy range of 12.8–120 MeV for Au and Bi elements. The experimental L X-ray spectra were analyzed using the method that takes into account the multiple ionization in outer shells. The L-subshell ionization cross sections have been obtained from measured X-ray production cross sections for resolved L
1,2 Lγ
1 and Lγ
2,3 transitions using the L-shell fluorescence and Coster–Kronig yields modified by the multiple ionization effects in the M and N shells. The results are compared with the predictions of ECUSAR theory, which is the modified ECPSSR approach describing both direct ionization and electron-capture processes and the semiclassical approximation (SCA) calculations for direct ionization. These approaches were modified by the L-subshell coupling effects within the “coupled-subshell model” (CSM). Both modified approaches are in good agreement with the data. Remaining discrepancies are discussed in terms of the L-shell decay rates modified for the multiple ionization effects.