Ice formation on surfaces is a serious issue in many different fields in terms of function, safety, and cost of operation in human life. Hydrophobic coating technology is one of the effective ways to prevent ice formation. Previous studies focused on the effects of surface structure and surface chemical modification on anti-icing ability. However, only a few studies have clarified a method to inhibit the initial formation of ice on surfaces; in addition, an effective mechanism for anti-frosting has not been identified as yet. Here, hydrophobic smooth surface coatings using three coupling agents with low surface energy and different molecular chain dynamics were fabricated. The surface roughnesses were lower than 1 nm.The fluorocarbon-based coatings delayed frost formation compared with the uncoated surface until À6 C. We explored why the coating surface prevented frost formation and the effects of surface chemical modification on frost resistance from the viewpoint of heat exchange contact area during droplet coalescence, ice nucleation free energy barrier, polarity and polarizability of the coated surface. † Electronic supplementary information (ESI) available: The chemical structure of decyltrimethoxysilane (DTMS), tridecauoro-1,1,2,2-tetrahydrooctyl-triethoxysilane (FAS13) and heptadecauoro-1,1,2,2-tetrahydrodecyl-triethoxy-silane (FAS17), FE-SEM image, FT-IR spectra, lm thickness distribution measured by ellipsometry analysis, transmittance measured by a spectrophotometer, total transmittance (TT), parallel transmittance (PT), diffusion (DIF) and haze values (HAZE) measured by a haze meter, the polarity factors of water, formamide and hexadecane, the polarity factors of the coating surface, photographic images of heating surface aer frosting test, the binarized photographic images during frosting test, the surface temperature with glass substrate and the coating surface, contact angle, sliding angle on the coating surface before freezing with aer freezing, classic heterogeneous nucleation theory, Hückel charge distribution of alkyl chain, uorocarbon and water molecular, the photographic images of frosting and water sliding angle of coating surfaces are changed molar ratio FAS to TEOS of solution, schematic image of measuring equipment of anti-frosting test. See