In this study, we present an N-heterocyclic carbene-catalyzed method for the radical acylphosphorylation of alkenes. Electrochemical investigations were employed to identify an appropriate class of oxime phosphonates capable of undergoing a single-electron transfer (SET) with Breslow enolates. The resulting phosphoryl radicals were effectively coupled with diverse styrenes and aldehydes to yield a variety of γ-oxo-phosphonates. Both radical clock experiments and electrochemical studies support our reaction design, and a plausible mechanism for the organocatalytic transformation is proposed.