Abstract A C( sp 3 )−H phosphorylation has been achieved via the iron‐catalyzed cross‐coupling reactions between 1,3‐dicarbonyl compounds and P(O)−H compounds involving C−C bond cleavages with air as the oxidant. This transformation provides a straightforward way to construct C( sp 3 )−P bonds, leading to the formation of β‐ketophosphine oxides in up to 93% yield with good functional group tolerance. magnified image