AbstractElectroinitiated polymerizations can be carried out by direct electron transfer if the anodic (Ep,a) and cathodic (Ep,c) potentials of monomers are known. Peak potentials of various halostyrenes were measured by cyclic voltammetry in acetonitrile for the first time. Polymerizations were carried out at measured peak potentials, on Pt0 electrode versus Ag0/Ag+, in dichloromethane in which chain transfer is negligible. Frontier molecular orbital energies εm and εm+1 of monomers were calculated by Hückel molecular orbital considerations. Measured Ep,a and Ep,c values were correlated to calculated HOMO and LUMO energies, respectively. Linear equations have been developed for the above correlations as well as for Ep,a — Ep,c versus εm — εm+1.