Abstract The first iron‐catalyzed oxophosphorylation of styrene derivatives with dialkyl H‐phosphonates under open air conditions is developed, which generates a range of previously underexplored α ‐substituted β ‐ketophosphonates in 55~70% yields. Furthermore, a convenient one‐pot procedure by direct conversion of styrenes to α , β ‐unsaturated ketones is also developed based on the new catalytic reactions, thus offering a protocol to access two classes of valuable products from simple starting materials.