Although POMs prepared in aqueous-organic solutions have been reported to exhibit interesting chemical properties and may be efficient catalysts, they could not be isolated in their protonated form using the normal extraction method. In this study, a new procedure of isolating protonated POMs, [S2VxM18-xO62]((4+x)-) and [AsVxM12-xO40]((3+x)-) (M = Mo, W; x = 0-2), which were prepared in an aqueous-organic mixed solution, was developed by modifying and optimising the extraction conditions. Isolated protonated POMs were characterised using IR and Raman spectroscopy, and their acidity was measured using a Hammett indicator. The acidity of H4S2W18O62, H5S2VW17O62, H4S2Mo18O62, and H3As2W18O62 was stronger than that of H3PW12O40. Their catalytic ability was investigated in multiple types of organic reactions, including pinacol rearrangement, acetal formation with benzaldehyde and ethylene glycol, and the Friedel-Crafts acylation of anisole with ethyl pyruvate. They exhibited greater catalytic ability than commercially available POMs such as H3PM12O40 and H4SiM12O40 (M = Mo, W). (C) 2014 Elsevier B.V. All rights reserved.