This study aimed to investigate the formation and alteration of tribofilm during pure rolling contact under sufficient lubrication. The surface state changes were also analyzed. Rolling contact experiments with varying stress cycles were conducted using a ball-rod testing machine. Characterizations on surface state including morphology, roughness and plastic deformation were executed and chemical composition and valence state of tribofilm were detected for different rolling periods. The results indicated tribofilm was formed and evolved due to the effect of Hertz Contact stress. Surface morphology changes and plastic deformation were caused by Hertz Contact, simultaneously. The micro-sliding destroyed the tribofilm to a certain degree, resulting in the change of surface state and tribofilm composition compared to the pure rolling region.