A new and general method for the synthesis of S-, Se-, and Te-aryl phosphorochalcogenoates (chalcogenophosphates) has been developed. S-P, Se-P, and Te-P bonds were formed by the coupling of readily available dialkyl phosphites with diaryl dichalcogenides at 30 ˚C in dimethyl sulfoxide in the presence of catalytic amounts of copper iodide and diethylamine. The reaction proceeded smoothly without exclusion of moisture or air.