This paper provides results on the tribological behavior of experimental Al–Sn–Pb–Si–Cu–Mg–Zn aluminum alloys and describes the adaptation phenomena that reduce wear intensity during friction with steel. The main focus is on tribofilm formation, which plays an important role in friction energy dissipation. The alloys were tested in a rig imitating a journal-bearing shaft couple, and the friction surfaces were studied by the scanning electron microscopy, energy-dispersive analysis and X-ray photoelectron spectroscopytechniques. Based on the analysis, a conclusion on processes and tribochemical reactions was made. Compared to the initial state, eight new compounds were found on the friction surface. In the most wear-resistant alloy, magnesium precipitated from a solid solution with the subsequent oxidation. The same process was detected for zinc in the least wear-resistant alloy due to its low magnesium content. Furthermore, CuSn3 and PbS compounds, which require >600 °C temperature to compose, were found in tribofilms, indicating that the rubbing body lost thermodynamic equilibrium during friction. The revealed processes are non-spontaneous and decrease the wear intensity of the alloys, as they are accompanied by negative entropy production and dissipation of friction energy. Stepwise depth XPS analysis also showed the functional levels of the tribofilms.