The effect of hydrogen bonding on both the kinetics and physical properties of photopolymerized thiol-ene systems has been determined by comparison of two thiol-ene systems, [butyl 3-mercaptopropionate/pentacrythritol tetrakis(3-mercaptopropionate)]/triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and [3-mercaptopropionic acid/pentaerythritol tetrakis(3-mercaptopropionate)]/triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. Hydrogen bonding in the thiol-ene network incorporating 3-mercaptopropionic acid leads to enhanced glass transition temperatures, refractive index, Persoz hardness, elastic modulus values, isothermal enthalpic relaxation, and rubbery-glassy heat capacity differences compared to networks formed using butyl 3-mercaptopropionate. Sub T-g aging analysis clearly shows that hydrogen bonding affects the isothermal enthalpic relaxation process.