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Silver exchanged silicotungstic acid (AgSTA) catalysts were prepared and characterized by X-ray diffraction, FT-IR spectroscopy, laser Raman, temperature programmed desorption of ammonia, FT-IR pyridine adsorption and X-ray photo electron spectroscopy. The activity of the catalysts was evaluated for the hydration of non-activated alkynes to corresponding carbonyl compounds without addition of any acid co-catalyst under solvent-free conditions. The highest catalytic activity was obtained for the catalyst with partially silver exchanged STA. This catalytic system provides one of the most straight forward syntheses of carbonyl compounds from terminal alkynes with Markovnikov-type regioselectivity. The catalyst can be recovered by simple filtration and is reusable without loss of activity and selectivity. A plausible reaction mechanism for the AgSTA catalyzed hydration of alkynes is proposed.