In this paper, both the TiB2/SiC bilayer films and the carbon-doped TiB2 (TiB2-C)/SiC bilayer films (SiC films as interlayer) were successfully deposited on quenched Cr12MoV steel substrate through magnetron sputtering technology, and the carbon-doping effect on microstructure and friction/wear properties of TiB2 films were investigated. The results show that the doped-carbon presented in manner of sp3C-C and sp2C-C bonds i.e. DLC (diamond-like carbon). As sliding against steel balls under dry frictional condition, the doped-carbon strongly decreased the friction coefficient of the films and the material transfer from the friction pairs to the films. At the same time, the doped-carbon reduced the wear rate of the films, the wear rate of the TiB2 films and the TiB2-C films were both in the magnitude order of 10−5 mm3 m−1 N−1, this is due to more material transfer significantly adhered on TiB2 films than on TiB2-C films.