Newly discovered N-heterocyclic carbene-boryl radicals (NHC-BH2 center dot) derived from readily available N-heterocyclic carbene-boranes arc found to be efficient initiators For acrylate photopolymerization. Laser flash phololysis (LFP) experiments were used to generate three carbene-boryl radicals, which were characterized by their transient absorption spectra with the aid of DFT calculations. Rate constants were measured for the generation of the carbene-boryl radicals by hydrogen abstraction with tert-butoxyl radical, a ketophosphonyl radical, and triplet benzophenone. Rate constants were also measured for the reactions of the carbene-boryl radicals with oxygen, three alkenes, two alkyl chlorides, and diphenyliodonium hexa-fluorophosphate. The observed trends were interpreted with the aid of measured oxidation potentials of the carbene-boranes and calculated ionization potentials of the carbene-boryls. N-Heterocyclic carbene-boranes show excellent potential as both photopolymerization co-initiators and mediators of small molecule radical reactions, and these results will help guide further development in both fields.