Phosphorus and its compounds are a cornerstone of biological life, as well as finding applications in material science, for example, as flame retardants, battery electrolytes or catalysts. In most applications, phosphorus-containing fine chemicals are in the naturally occurring and most stable oxidation state +V of the element; however, syntheses to these compounds from primary P^V sources rely on an energy-consuming and wasteful redox detour via elemental white phosphorus (P₄) and its subsequent (oxy)chlorination to PCl₃, PCl₅ and POCl₃. Here we report an approach using trifluoromethanesulfonic anhydride (Tf₂O) and pyridine to directly cleave P–O bonds in ubiquitous P^V sources to form the versatile PO₂⁺ phosphorylation agent (pyridine)₂PO₂[OTf] (1[OTf]), whose preparation and mechanism of formation is discussed. Harnessing its reactivity towards various nucleophiles such as amines, alcohols and pseudohalogenides, 1[OTf] then provides redox-neutral access to a range of value-added P^V chemicals downstream of low-cost phosphoric acid or other phosphate sources. [Figure not available: see fulltext.].