Selectively catalyzed dehydration of ethanol, 1,2-propylene glycol, and glycerol on supported heteropoly acid (HPA) was studied using transient diffuse reflectance infrared fourier transform spectroscopy (DRIFTS). Tungstosilicic acid (H-4[SiW12O40] denoted as H4SiW), supported on neutral mesoporous alumina as a catalyst, was studied to investigate the formation of intermediate products and desired dehydration products on the catalyst surface. Both ethylene-containing species and surface-bound carboxyl species were detected for all three alcohols. The formation of ethylene was promoted at lower temperatures while an increased reaction temperature facilitated the formation of acetate products when ethanol was used. When 1,2-propylene glycol was used, surface-bound carboxyl species were found as major intermediate products; these might have formed from propanal produced from the hydration reaction catalyzed by acid sites on HPA. Intermediate species from more complicated reactions were detected on the catalyst surface when glycerol was used, including aldehyde, surface-bound carboxyl species, and alkene species. The results indicated that acid dehydration might be facilitated either by the addition of water or lowering the reaction temperature. The work provides insight into reaction pathways for bio-polyols, and therefore is informative for designing cost-effective and efficient chemical catalysis systems for the conversion of bio-renewables.