The construction of silicon-containing molecules has received increasing attention in recent years. Herein, we report the generation of silyl radicals through NHC catalysis under mild reaction conditions. This methodology offers a novel and convenient route to a diverse range of β-silyl ketones with a broad substrate scope and good functional group compatibility. Both the radical clock and electrochemical studies are consistent with the hypothesis of ground-state SET, and a plausible mechanism for the organocatalytic transformation is proposed.