AbstractResearch on the boundary lubrication performance of two perfluoropolyether (PFPE) thin films in the presence of passirated 440C stainless steel is presented. The study used a standard ball‐on‐disc (BoD) tribometer operating in dry nitrogen and a vacuum spiral orbit tribometer (SOT). Stainless steel surfaces were passivated using one of four techniques: a high‐temperature and low‐temperature chromic acid bath, a tricresyl phosphate (TCP) soak, or UV/ozone treatment for 15 min. After passivation, each BoD disc had a 400 Å film of Krytox® 16256 (PFPE) applied to it. The lives of these films were quantified by measuring the number of sliding cycles before an increase in friction occurred. The lubricated life of the 440C couple was not altered as a result of the various passivation techniques. The resulting surface chemistry of each passivation technique was examined using X‐ray photoelectron spectroscopy. The SOT was used to examine the effects of the TCP treatment on the lubricated life of another PFPE, Brayco® 815Z, under rolling conditions. None of the passivation techniques were found to increase dramatically the oxide film thickness or lub