Triarylphosphines play a crucial role in organic synthesis as versatile components serving as ligands, catalysts, and reactants. This study introduces a metal-free, visible-light-induced method for the cross-coupling of cyanopyridines or polyfluoroarenes with diarylphosphines. This approach facilitates the formation of C(sp2)-P bonds through redox-neutral decyanative or defluorinative process, enabling the convenient synthesis of diverse triarylphosphines.