WVOx bi-metal oxides supported on the cost-effective industrial mesoprous Al2O3, SiO2, active carbon (AC), and TiO2-Al2O3 with different specific surface areas (WVO/Al2O3, WVO/SiO2, WVO/AC, and WVO/TiO2-Al2O3) were designed and prepared through co-impregnation method for large-scale bio-glycerol dehydration to acrolein. The XRD, BET, SEM-EDS, XPS, and NH3-TPD characterization results revealed the WO3-VOx (V4+/V5+) species existed with better dispersion, lower molar ratio of V4+/V5+, and enhanced strength of surface acid sites on the developed mesoporous TiO2-Al2O3 in comparison with that on the mesoporous Al2O3, SiO2, and AC, demonstrating strong interaction of WO3-VOx species with the TiO2-Al2O3 support and accounting for the acrolein selectivity over catalysts following the order of WVO/TiO2-Al2O3 (75.8%) > WVO/AC (71.2%) > WVO/SiO2 (55.3%) > WVO/Al2O3 (42.8%). Over the WVO/TiO2-Al2O3, gas-glycerol conversion reached above 97.0% with acrolein selectivity of about 75.0% under the gas hourly space velocity (GHSV) of 120-360 h(-1), and maintained an improved catalytic stability. [GRAPHICS]