Quantitative analysis of materials from Heavy Ion PIXE spectra remains impeded by the lack of reliable X-ray production cross section (XPCS) data. Although efforts at experimental Heavy Ion induced XPCS measurements still continue, Multiple Ionisation (MI) effects, which are not fully described by theory, render simulations of heavy ion PIXE data unreliable for large Z1/Z2 collisions, especially at low energies. This is also exacerbated by the random selection of projectile-target combinations for measured and reported experimental data available to validate theory. This study explored heavy ion induced X-ray production cross section deviations from those induced by protons at the same ion velocity. This enabled evaluations of the degree to which cross sections are enhanced through MI effects, with the aim of predicting XPCS due to heavy ion impact. The evaluation was carried out through the scaling of experimental heavy ion to theoretical proton cross section ratios (R), which were then used for the interpolation of XPCS in the same target element for ‘missing’ projectiles within the range of evaluation. Here we present measurements of heavy ion induced total L-shell XPCS in Bi, carried out to determine HI/p MI induced deviations due to C, F, Cl and Ti projectiles at an ion velocity range of (0.2–1.0) MeV/nucleon.