The tribological behavior of carboxylic acids, especially oleic acid, in boundary lubrication conditions is a subject of interest. This study presents the results of four-ball tribological tests conducted under varying contact pressures and sliding speeds. The findings reveal a critical turning speed within a confined zone, which causes a significant change in the frictional performances of oleic acid, leading to the formation of an ultralow wear tribofilm. This tribofilm, predominantly composed of oxyhydrogen compounds and hydrocarbons with more than five carbon atoms, is generated by the molecular action of oleic acid. Reactive nonequilibrium molecular dynamics simulations demonstrate that the shear speed-dependent decomposition modes of oleic acid and the transformation of the lubrication slip interface are the fundamental processes underlying the formation of this ultralow-wear boundary tribofilm.