Tribochemical reactions between Si incorporated diamond-like carbon (Si–DLC) films and steel ball were investigated during initial stage of tribo-test. The films were deposited by r.f.–PACVD using mixtures of diluted silane (SiH4:H2=10:90) and benzene gases. Si concentration in the film was varied from 0 to 10 at.% by adjusting the diluted silane fraction in the reaction gases. A rotating type ball-on-disk wear rig was employed for the tribo-test in ambient atmosphere. When the Si concentration was less than 5 at.%, initial transient period of high friction coefficient was commonly observed. After the transient period, the friction coefficient becomes lower with increasing contact cycles. The initial transient period becomes shorter and the starting and maximum friction coefficients in transient period decreased with increasing Si concentration. Composition of the debris on the wear scar surface was analyzed by Auger spectroscopy at various stages in the initial transient period. We observed that when the friction coefficient increased in earlier stage of the transient period, iron and oxygen was observed in the debris. However, decrease in the friction coefficient in the later stage of the transient period was associated with the formation of silicon rich oxide debris. This result supports the friction mechanism of Si-DLC films that the formation of Si rich oxide debris results in low friction coefficient in ambient atmosphere.