In this study, tribological properties of hydrogenated and hydrogen free diamond-like carbon films at various relative humidity (RH) were investigated to understand the friction mechanism in the presence of water molecules. At normal load of 2N, DLC-H film's friction coefficient was 0.06 at RH14% while DLC film's friction coefficient was 0.19 at RH17%. With the increase of RH, their friction coefficient converged to about 0.15. This character remained unaltered when the normal load was 5N. Results show that low friction of DLC-H film at low RH was attributed to the low shear force aroused by graphitic tribofilm at wear care center. However, the high friction of DLC film was mainly endowed by the high adhesive force aroused by sigma dangling bonds. At high RH, solid-to-solid contact was isolated by water molecules confined between the counterfaces, where capillary was a dominant factor for friction. In addition to the capillary force, the absence of tribofilm was also accountable. These two factors lead to the level off of friction coefficient for DLC-H and DLC films. Moreover, for both DLC-H and DLC films, tribo-oxidization was proved to be closely related to wear rate with the assist of H₂O molecules during sliding.