A dual-layer film composed of alkylsilane with amino groups and semi-spherical molecules was constructed on silicon substrate by a two-step strategy. 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (TA) was self-assembled on silicon surface to form amino-terminated underlayer, followed by deriving with hexachlorotribenzotriquinacene (HCTQ) through surface coupling reaction to form the second layer. The formation and structure of the as-prepared films were analyzed, and the nano- and micro-tribological properties were estimated, respectively. The results showed that the dual-layer film possesses excellent friction-reducing and anti-wear abilities, which is attributed to the combination of enhanced stability by hydrogen bonding and the high stiffness of rigid outer layer. In other words, the cross-linked underlayer with internal hydrogen bonds enhances the stability of the film against rubbing the counterpart ball, and the rigid backbone in HCTQ molecules improves the load-carrying capacity of the dual-layer film. High wear stability along with superior load-carrying capacity made these molecular films very promising as a new generation of molecular lubricants for MEMS/NEMS.