Addn. of TPA.Cl (TPA = tetra-n-propylammonium) to a reaction mixt. of H2WO4, H2O2, and HCl gave a novel all-inorg. mononuclear chloro oxo diperoxotungstate, TPA[WOCl(O2)2(H2O)] (I), which was characterized by x-ray crystallog., elemental anal., and IR, Raman, UV-vis, 17O and 183W NMR spectroscopies, and CSI-MS. Compd. I acted as a good precursor for the high-yield synthesis of an active protonated tetranuclear peroxotungstate, TPA3[H{W2O2(O2)4(ホシ-O)}2]. [on SciFinder(R)]