Tribo-chemical studies of the lubricant thickness effect on the tribology of the head/disk interface (HDI) were conducted using hydrogenated (CHx) carbon disk samples coated with perfluoropolyether ZDOL lubricant. The studies involved drag tests with uncoated and carbon-coated Al2O3–TiC sliders and thermal desorption experiments in an ultra-high vacuum (UHV) tribochamber. The studies showed that the lubricant interaction with the carbon overcoat varies as a function of lubricant thickness. Wear durability improves considerably for thicknesses more than a monolayer. However, in the sub-monolayer thickness regime, the adhesion of the lubricant to the carbon overcoat is much stronger, as indicated by the fact that a much higher temperature is required to desorb the lubricant. When the lubricant thickness is around or above a monolayer, cohesion among the lubricant molecules plays a greater role and a much lower temperature is needed for lubricant desorption.