Stable acrylate/triethoxyvinylsilane (VTES) core–shell emulsion with different mass ratio of MMA/BA in the core and shell was prepared via a modified micro-emulsion polymerization process. The chemical composition and core–shell structure were investigated by Fourier transform infrared (FTIR) spectrometry, differential scanning calorimetry (DSC) and transmission electron microscopy (TEM), respectively. Effect of MMA/BA mass ratio in the core and shell on the film-forming ability, surface tension of latex was also studied. Finally, water absorption and thermal stability of the latex films were characterized. It was found that the surface tension of emulsion can be reduced to 32.9N/m when the MMA/BA mass ratio in the shell is 6/4. The water absorption of the latex film could be improved at a proper mass ratio of MMA/BA in core and shell, but adjusting the mass ratio of MMA/BA in the shell has little influence on the thermal stability of latex film. This work provides a method of preparing environment-friendly latex with low surface tension and excellent water resistance for coating applications by regulating the mass ratio of monomers in a modified micro-emulsion polymerization process.