UV/ozone (UVO)-assisted formation of self-assembled monolayer (SAM) of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDS) was prepared on a glass surface. The effect of UVO exposure time on surface roughness and hydrophilicity was investigated through goniometer and atomic force microscope (AFM), and deposition time-dependent SAM quality was detected by AFM and X-ray photoelectron spectroscopy (XPS). The glass surface became smooth with UVO radiation after 10 min, and the hydrophilicity was also improved after the treatment. Confirmed by surface topography detection and chemical composition analysis, a high-quality SAM can be formed rapidly on glass with 10 min UVO treatment followed by 2 h deposition in PFDS solution. Excellent tribological performances of SAM coated with UVO treatment glass were demonstrated by friction and wear tests on AFM compared to film-deposited glass without UVO treatment and original glass. The study sheds a light on preparing high-quality lubrication and antiwear self-assembled films on the surface of engineering materials.