A combined experimental and computational study of the reactivities of seven commonly used Michael acceptors paired with two thiols within the framework of photobase-catalyzed thiol-Michael reactions is reported. The rate coefficients of the propagation ( k P ), reverse propagation ( k -P ), chain-transfer ( k CT ), and overall reaction ( k overall ) were experimentally determined and compared with the well-accepted electrophilicity parameters of Mayr and Parr, and DFT-calculated energetics. Both Mayr's and Parr's electrophilicity parameters predict the reactivities of these structurally varying vinyl functional groups well, covering a range of overall reaction rate coefficients from 0.5 to 6.2 s −1 . To gain insight into the individual steps, the relative energies have been calculated using DFT for each of the stationary points along this step-growth reaction between ethanethiol and the seven alkenes. The free energies of the individual steps reveal the underlying factors that control the reaction barriers for propagation and chain transfer. Both the propagation and chain transfer steps are under kinetic control. These results serve as a useful guide for Michael acceptor selection to design and predict thiol-Michael-based materials with appropriate kinetic and material properties. A systematic investigation extends the fundamental understanding of the structure-property relationships between vinyl functionality and the reaction kinetics for the thiol-Michael reactions.