A metal‐free and oxidant‐free protocol for oxidative coupling of quinoxalin‐2(1H)‐ones with diarylphosphine oxides and pyrroles via electrochemical dehydrogenation has been reported. A broad range of C3‐functionalized products were obtained in good to excellent yields. Synthetic methods: A metal‐free and oxidant‐free protocol for oxidation of quinoxalin‐2(1H)‐ones with diarylphosphine oxides and pyrroles via electrochemical dehydrogenation has been reported. Featured by readily available substrates, simple electrolysis conditions and wide scope of substrates, this protocol provides a straightforward and green way toward C−P, C−C(sp2) bonds construction.