An environmentally friendly and resourceful modular protocol for the synthesis of phosphorochalcogenoates, phosphorochalcogenothioates, and phosphinothioates under blue light-emitting diode irradiation is described. The blue LED-promoted P−S, P−Se, and P−Te bond constructions occurred under metal-free, ligand-free, oxidant-free, and photocatalyst-free conditions with minimum chemical waste generation and high atom economy providing the resulting phosphorochalcogenoates, phosphorochalcogenothioates, and phosphinothioates in good to excellent yields.