In this study, epoxidized soybean oil was modified to prepare acrylated epoxidized soybean oil (AESO) and vinyl/acrylate ended soybean oil (VASO), which were blended with mercaptopropyl polyhedral oligomericsilsequioxane (POSS‐SH) to prepare UV curable thiol‐acrylate and thiol‐ene‐acrylate hybrid coatings. Photopolymerization processes of the coatings were measured and the results showed that addition of POSS‐SH obviously increased the conversion of double bond. The physical and mechanical properties of all cured samples were investigated, which indicated that the pencil hardness, tensile strength, and fracture toughness were significantly improved by POSS‐SH. Moreover, with increasing POSS‐SH content, the water contact angles of cured samples were increased, and the water resistance was greatly improved. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42095.