A DMSO-catalyzed double P-O bond or double P-S bond formation of phosphinic acid with an O- or S-containing nucleophile has been developed. Under metal-free and mild conditions, this simple procedure provides a compatible and rapid access to a variety of phosphonates and dithiophosphates. The DFT calculation of stabilization energy (SE) and the mechanism studies demonstrated that the "just right" Lewis base property and the relatively "soft" interaction strength with the phosphenium-dication ensure the unique catalytic activity of DMSO in this transformation.