In this study, octyl-triethoxysilane emulsion was prepared using octyl-triethoxysilane monomer. The protective effect of the silane monomer and emulsion was investigated on the concrete with different water to cement ratios (0.4 and 0.5). The results showed that octyl-triethoxysilane emulsion displayed efficient protection of concrete. Octyl-triethoxysilane emulsion acquired excellent penetration depth (> 3.7 mm), the water absorption coefficient was reduced by 83.4%, and the chloride ion diffusion coefficient was only 1.8 × 10−12 m2 s−1, reduced by 71.3%. The emulsion also showed good resistance to carbonization and freezing-thawing. The carbonation depth of concrete was reduced by 42%, while the silane monomer has little effect on carbonization. Good protection performance was obtained in the freezing-thawing cycle tests. The relative dynamic elastic modulus was increased by 27%; the mass loss was reduced by 49% after 300 cycles. The protective effect of silane emulsion was also related with the water cement ratio of concrete and the test method. Silane monomer had good waterproof effect and chloride resistance, but poor resistance to carbonization and freezing-thawing. Silane emulsion was a better choice for concrete protection, for it displayed lower rate of volatilization, insignificant toxicity, and better retainment of the active ingredient.