In this work, we evaluated the effect of the counter-body material (the same or dissimilar) and contact configuration (moving or stationary body), at similar contact tribological conditions, on the tribochemical and nanotopography characteristics of adsorbed surface films. Zinc dialkyldithiophosphate (ZDDP), the best performing anti-wear additive, was used in self-mated steel/steel and DLC/DLC contacts, which were compared with mixed steel/DLC and DLC/steel contacts in 1-h and 6-h sliding tests. The macroscale (tribometer) and nanoscale (atomic force microscopy) friction, thickness, topography, and chemical (attenuated total reflection-Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy) properties of the tribofilms were studied. The results revealed unexpectedly large differences in all the studied tribofilm parameters; this is because all the tribofilms are completely different; this includes the chemical composition, which is known to have a crucial effect on the nano- and macro-scale tribological properties. These results clearly demonstrate that the surface material, additives, and common contact operating parameters, that is, pressure, velocity, and temperature, crucially affect the ZDDP tribofilm as well as the position of the moving or stationary surface within the contact, and the material of the moving/stationary bodies.