Anti-stiction coatings for silicon surfaces are a key technology to prevent the failure of nanoelectromechanical systems (NEMS) during operation and improve the forming accuracy in nanoimprint technology. In this study, we propose an atmospheric vapor phase deposition method to coat a silicon surface with fluoropolymers such as the perfluoropolyethers Fomblin Zdol 2000 and Zdol 4000. Thickness distributions, surface energies, coverages, and stiction forces for the deposited films were evaluated experimentally. The proposed method resulted in over 90% coverage with a film thickness of about 1 nm. The film thickness uniformity was around 0.1 nm over an area of 5 × 5 mm2. This coating effectively reduced the stiction forces by half compared with a bare silicon surface.