Dialkyl(heteroaryl)phosphine sulfides were synthesized by the rhodium‐catalyzed exchange reaction of heteroaryl aryl sulfides and tetraalkyldiphosphine disulfides. The reaction has a broad applicability, giving diverse dialkyl(heteroaryl)phosphine sulfides containing five‐ and six‐membered heteroaryl groups. Various dialkyl(heteroaryl)phosphines were obtained by desulfurization.