A clean and direct aerobic oxyphosphorylation of terminal alkynes with dialkylphosphine oxides has been developed using only visible light and air at room temperature. The method provides a highly simple, efficient, economic and environmental-friendly approach to prepare valuable β‑ketophosphine oxides in satisfactory yields. Control experiments revealed that the O2 can initiate phosphinoyl radicals through single electron transfer (SET) oxidative activation with the synergistic role of light.