In peroxymonosulfuric acid, the S(VI) center adopts its characteristic tetrahedral geometry; the connectivity is indicated by the formula HO–O–S(O)2–OH.

[4] The German chemist Heinrich Caro first reported investigations of mixtures of hydrogen peroxide and sulfuric acid.

[5] One laboratory scale preparation of Caro's acid involves the combination of chlorosulfuric acid and hydrogen peroxide:[6] Patents include more than one reaction for preparation of Caro's acid, usually as an intermediate for the production of potassium monopersulfate (PMPS), a bleaching and oxidizing agent.

It is used in gold mining to destroy the cyanide in the waste stream ("Tailings").

As with all strong oxidizing agents, peroxysulfuric acid is incompatible with organic compounds.