The wear and friction of diamond-like nanocomposite (DLN) film have been investigated in air with different relative humidity (RH), under deionized (DI) water and saline solution. The structure of the film has been characterized by Fourier transform infrared (FTIR), Raman spectroscopy, and scanning electron microscope (SEM). The result shows two interpenetrating network structure: a-C:H and a-Si:O, and they are interpenetrated by Si-C bonding. The tribological performance has been measured using ball-ondisc tribometer with tungsten carbide ball as counterbody at 10 N normal load. Results show that with increasing relative humidity (RH) from 35% to 80%, the coefficient of friction (COF) increases gradually from 0.005 to 0.074, whereas with increasing RH the wear factor decreases from 9.8 × 10 −8 mm 3 /Nm and attains a minimum value of 2.7 × 10 −8 mm 3 /Nm at 50% RH. With further increase of RH the wear factor increases again. Moreover, in DI water and especially in saline solution, both the COF and wear factor have been found to be significantly low. A clue has been interpreted to understand environmental dependency, considering the effect of surface dangling bonds, charge transfer, and chemical interactions.