Three 3-mercaptopropionate thiols, 1,6-Hexane bis(3-mercaptopropionate) (HD-SH), trans-1,4-Cyclohexanedimethyl bis(3-mercaptopropionate) (CHDM-SH), and 4,4'-Isopropylidenedicyclohexane bis(3-mercaptopropionate) (HBPA-SH) were formulated with 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO) and photoinitiator. The formulations were photopolymerized via thiol-ene photopolymerization. A ternary experimental design was employed to elucidate the influence the three thiols on the thermomechanical and coatings properties of thiol-ene photopolymerizable materials. Tensile strength, tensile modulus, elongation-to-break, glass transition temperature (T-g), and crosslink density (XLD) were investigated. Coating properties including pencil hardness, pull-off adhesion, MEK double rubs, and gloss were also investigated. Relative reaction conversion was determined by photo differential scanning calorimeter (PDSC). Thiol-ene photopolymerizable materials containing HBPA-SH resulted in improving tensile strength, tensile modulus, T-g, and pencil hardness but lowering of crosslink density and relative conversion. This was attributed to steric and rigidity of the double cycloaliphatic structure. The inclusion of CHDM-SH into the systems resulted in the synergistic effect on elongation-to-break and pull-off adhesion. The HD-SH generally resulted in a diminution of thermomechanical and coating properties, but improved the crosslink density. (C) 2009 Wiley Periodicals, Inc. J Appl Poly in Sci 113:2173-2185, 2009