Photopolymerization systems based on hybrid monomer 3,4-epoxy-cyclohexylmethyl methacrylate (METHB) were studied to investigate water effects on conversion and polymer coating properties. METHB contains epoxide and methacrylate moieties, which undergo cationic and free-radical photopolymerization, respectively. The conversion of both groups was obtained by Raman spectroscopy in real time and depth. Water concentration and initiator system compositions were varied and shown to affect reaction kinetics and depth profile. With increasing water concentration, the epoxide induction period increased when only cationic initiator was present; however, the induction period disappeared when using the dual-initiator system. In addition, epoxide groups continued reacting after light was shuttered and reached a higher and more homogeneous conversion. Hybrid systems were shown to be less sensitive to water at low or intermediate concentrations. With high water concentrations, hybrid monomer systems manifested increased ring opening during illumination due to chain transfer and decreased physical properties due to loss of cross-linking. (C) 2009 Elsevier Ltd. All rights reserved.