The copper-catalyzed radical multi-component coupling of maleimides, anilines, and diarylphosphine oxides has been realized, providing the rapid synthesis of a library of aminophosphinoylated maleimides, with the formation of C–N and C–P bonds. The remarkable feature of the current multi-component reaction was that five clinical drug molecules containing sulfonamide and arylamine functional groups underwent chemo-selective radical vinylphosphinoylation to access sterically congested products. Most impressively, this transformation worked on a wide range of substrates and showed good functional group tolerance.