Phosphorus-substituted heterocycle compounds, owing to their unique structural features and pharmacological activities, have gained significant attention.1 Among them, the phosphorus-centered radical-initiated cascade reaction is undoubtedly an effective avenue to construct phosphorus-containing heterocycle compounds.2 Conventional synthetic strategies for the formation of phosphoryl radicals largely depend on the use of transition metal salts at elevated temperatures or required typical photocatalysts including noble-metal-based photocatalysts or unrecyclable organic dyes, thus limiting their practical applications. Recently, we developed a visible-light-induced metal-free peroxide-promoted cascade phosphorylation reaction to access various phosphorylated benzazepino[1,2-a]indolone at room temperature.