We present in this paper, M‐shell ionization cross sections and M X‐ray production cross sections calculated within the Energy loss, Coulomb deflection, Perturbed Stationary State and Relativistic effects (ECPSSR) theory for elements with 72 ≤ Z ≤ 90 for protons with 0.1–4.0 MeV energy. Our results are compared to the plane wave Born approximation (PWBA) predictions, the relativistic plane‐wave Born approximation including corrections for binding and Coulomb deflection effect (RPWBA‐BC) results and the ECPSSR calculations from earlier works. On the other hand, semiempirical and empirical M X‐ray production cross sections are deduced from the polynomial fitting of the available experimental data collected from different sources. A comparison is made between the different sets of results. The differences between the above calculations and the experimental results are pointed out and discussed. Copyright © 2009 John Wiley & Sons, Ltd.