A peptide-containing alkylsilane self-assembled monolayer on silicon surface has been prepared successfully by a simple one-step strategy. The formation and structure of the peptide-containing SAMs were characterized by means of contact angle measurement, ellipsometry, FT-IR, and AFM morphology observation. It was found that the water content in the hydrolysis solution plays a key role in determining the quality of the monolayers. The micro-tribological properties of various films were evaluated by using AFM, while the macro-tribological study was performed on a ball-on-plate tribometer. It was found that the peptide-containing monolayers possess excellent friction-reduction and antiwear ability, which was attributed to its amide-containing structure. In other words, the interchain hydrogen bonds among the molecules enhance the stability of the monolayers against rubbing the counterpart ball and thus endow it an outstanding antiwear ability.