The combination of silanes and enes yields highly reactive photopolymerizable mixtures that exhibit very low oxygen sensitivity. Diphenylsilane (SiH) has been used in combination with different multifunctional acrylates (AC) and conversions of 100% and about 25% for AC and SiH, respectively, have been reached. Final tack free polymers are obtained as a consequence of the fact that the polymerization rates are not affected by oxygen. When using vinylacetate (VA), divinylether (DVE), and allylether (AE) units, the final silane conversion still remains low (50, 20, and 20%, respectively) but are promising. The reactivity of the silyl radicals is investigated by laser flash photolysis. The role of the bond dissociation energy of the silane is outlined.