This article focuses on the principles and applications of thermal desorption spectroscopy (TDS) use to study adsorption, desorption, and reaction of adsorbed atoms and molecules on surfaces. The discussion provides information on various components of and specimen preparation processes for a TDS experiment. The factors that must be considered when performing TPD experiments and several methods of analyzing TPD data are covered. A few studies where TPD was used to elucidate surface reactions that impact the tribological performances of materials are also discussed.