In situ analyses of lubricated sliding contacts were performed by interfacing an ultraviolet Raman spectrometer to a ball-on-flat tribotester. The sliding contact was simulated by rotating a sapphire window that is transparent to ultraviolet radiation against a stationary ball. Various loads were transmitted to the contact center through the ball. A branched perfluoropolyaklyl ether (Krytox 479) and two linear perfluoropolyalkyl ethers (Fomblin 491 and Fomblin 497) have been studied under various loads at a 10 cm/s sliding speed. Krytox and a Fomblin of lower viscosity, Fomblin 497, decomposed to amorphous carbon upon sliding on a chrome steel ball but no amorphous carbon was detected from Fomblin 491. The amount of amorphous carbon at the contact area during sliding was a balance of formation and removal rates. It is postulated that surface activity of the chrome steel ball was the main cause for the lubricant degradation. The lubricant degradation at the chrome steel/sapphire interface was found to slightly increase the kinetic coefficient of friction at the contact center. However, catastrophic scuffing was not observed.