Functional polydimethylsiloxanes containing vinyl groups (Vi‐PDMS) were used for silicone‐based organic polymers in composites and adhesive formulations. Poly(butyl acrylate/methyl methacrylate/vinyl silicone oil)/casein–caprolactam [P(BA‐MMA‐Vi‐PDMS)/CA‐CPL] nanoparticles were prepared via emulsifier‐free polymerization. The well‐defined core–shell structure of P(BA‐MMA‐Vi‐PDMS)/CA‐CPL nanoparticles was verified by transmission electron microscopy. The results of scanning electron microscopy and contact angle measurements proved that the as‐obtained coatings exhibited porous and hydrophobic properties, which were helpful for superior water vapor permeability. By comparing the appearance of the coatings before and after adhesion analysis, the excellent adhesion strength was proved to be dominated by Vi‐PDMS. The relationship between interface morphology and properties of the resultant coatings was investigated in detail. The nucleation mechanism for this soap‐free emulsion synthesis was also proposed accordingly. These results could help in designing coatings with better surface properties and wider application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46501.