Sulfur-containing organophosphorus molecules have played a pivotal role in organic synthesis, pharmaceutical pesticides and functional materials, thereby motivating researchers worldwide to establish S–P bonds from more environmentally friendly phosphorus sources. In this study, a novel method was developed for constructing S–P bonds, specifically by reacting the inorganic phosphorus derivative TBA[P(SiCl₃)₂] with sulfur-containing compounds under mild conditions. This method demonstrates the advantages of low energy consumption, mild reaction conditions and environmental friendliness. Moreover, this protocol—as a green synthesis method to replace the use of white phosphorus in the production of organophosphorus compounds (OPCs)—achieved the functional conversion of “inorganic phosphorus to organic phosphorus”, in line with the national green development strategy.