The fourth generation of poly amide amine molecular self-assembled monolayer (PAMAM (G4.0)-SAM) was prepared on hydroxylated Si (111) substrate by a self-assembled technique from specially formulated solution. The PAMAM (G4.0)-SAM were characterized by means of contact angle measurement, ellipsometry, X-ray photoelectron spectroscope (XPS), and atomic force microscopy (AFM). The tribological properties of the as-prepared thin films sliding against a steel ball were evaluated on a friction and wear tester. The tribological results show that the friction coefficient of monocrystal line silicon substrate reduces from 0.6 to 0.18 due to the formation of PAMAM-SAMs on its surface. And the PAMAM (G4.0) -SAM has longer wear life (18000 sliding pass). It is demonstrated that PAMAM (G4.0) -SAM exhibited good wear resistant property. In conclusion, the PAMAM (G4.0)-SAM which possesses good wear resistant property was successfully prepared and the film.