X‐ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) were used to identify gas reaction layers and tribochemical films formed during reciprocating sliding tests in an ultrahigh vacuum (UHV) tribometer. Tests were performed on UHV cleaned SiC pins and Mo flats during or after exposure to SO2, O2, or H2S gas at pressures around 40 Pa. XPS identified the gas reaction layers on Mo to be chemisorbed MoS2and/or MoO2phases less than 1 nm thick. AES of Mo wear tracks showed tribochemical films similar in composition to, but thicker than, the reaction layers. AES of SiC wear scars in all three gases indicated tribochemical films containing Si oxide and/or Si sulfide and possibly graphite. In addition, transfer films of Mo oxysulfide and Mo oxide were found in SO2and O2tests, respectively, but no transfer films were detected in H2S tests. Thermochemical calculations of stable reaction products of the gas–solid reactions were in good agreement with the phases inferred from XPS and AES. An explanation for the agreement between thermochemical predictions and tribochemical results is given.