A series of supported silicotungstic acid (H4SiW12O40 center dot xH(2)O) catalysts was prepared from selected silica and alumosilicate carriers. Alkaline metals lithium, potassium and caesium were added to modify catalyst Bronsted acidity. Physico-chemical characterisation of the catalysts was carried out with nitrogen adsorption (BET), X-ray diffraction (XRD), and infrared (IR) and Raman spectroscopy and revealed that the nature of the alkaline metal is significant for (i) specific surface area which rises with metal ion radii and (ii) dispersion of active compound formed from alkaline metal and silicotungstic acid on the support surface. Interestingly, acidic properties rather do not depend on nature of alkaline metal. The catalysts were catalytically evaluated at standardised reaction conditions in a continuous flow lab scale set-up (10 wt.% of glycerol in water, 225-300 degrees C, modified contact time 0.15 kg h mol(-1)). Among the tested supported catalysts, lithium exchanged H4SiW12O40 center dot xH(2)O showed highest activity and maximum selectivity of 70% for acrolein at complete conversion. Main effect of alkaline metal addition can be seen in improved selectivity and activity, in particular with silica supported catalysts. (C) 2010 Elsevier B.V. All rights reserved.