Various properties of UV-initiated acrylate/ epoxide and acrylate/vinyl ether hybrid photopolymerizations with and without photosensitizer in the presence of free radical and cationic-type photoinitiators have been determined by dynamic mechanical thermal analysis (DMTA), calorimetric analysis (photodifferential scanning calorimetry, photo-DSC; and differential scanning calorimetry), and scanning electron microscopy. DMTA experiments revealed that the UV curing of hybrid systems may produce interpenetrating polymer networks. Photo-DSC analyses indicated that the acrylates polymerized faster than the epoxide and vinyl ether in the hybrid systems; the addition of a photosensitizer, isopropylthioxanthone (ITX), increased the polymerization rate of the epoxide and vinyl ether in the hybrid systems. SEM analysis confirmed that the free radical system seemed to be significantly affected by oxygen inhibition, while the cationic and hybrid systems were not nearly inhibited by oxygen; the presence of photosensitization produced by the addition of ITX enhanced the surface curing of the hybrid systems. (C) 2004 Wiley Periodicals, Inc.