Peroxyphosphoric acids were first synthesized and characterized in 1910 by Julius Schmidlin and Paul Massini via the reaction between phosphorus pentoxide and highly-concentrated aqueous solution of hydrogen peroxide.

A less vigorous method of preparing peroxyphosphoric acid by introducing the inert solvent acetonitrile was described by Gerrit Toennies in 1937.

[2] Peroxyphosphoric acid is usually produced by treating phosphorus pentoxide and concentrated hydrogen peroxide within an inert solvent like acetonitrile or carbon tetrachloride.

In aqueous solutions it slowly undergoes hydrolysis to hydrogen peroxide and phosphoric acid.

[7] A solution in acetonitrile also slowly degrades, losing 30% of active oxygen after 26 days of storage at 5 °C.

[3] They have been examined in the context of organic synthesis, as an electrophilic reagent for the oxidation of alkenes, alkynes, aromatic compounds and amines.

[8] The oxidation of diphenylacetylene at room temperature yields benzil, presumably through an oxirene intermediate.