Acrolein, a crucial precursor to acrylic acid, is traditionally produced via propylene oxidation. This work investigates a more sustainable approach: acrolein production from glycerol dehydration using hydrothermally synthesized mesoporous hexagonal tungsten oxide (h-WO3) catalysts. While h-WO3 offers high selectivity for acrolein, its stability presents a challenge. We addressed this by optimizing the crystal phase through controlled hydrothermal methods and enhancing porosity with co-surfactants, improving mass transfer. The prevalent hexagonal tungsten bronze (HTB) phase in the investigated catalysts is demonstrated to enhance activity compared to traditional monoclinic WOx. Moreover, the mesoporous structure of the catalysts facilitates mass transfer and active site accessibility, enhancing glycerol dehydration performance. Optimization of the synthesis process, incorporating varied hydrazine ratios and tungsten starting salts, refines catalyst properties. Structural characterization explicates variations in lattice W-O bond types and acidity, correlating with catalytic behavior. The resulting mesoporous HTB catalysts exhibit high efficiency, achieving acrolein yields of up to ∼100 %, along with notable stability, maintaining selectivity above 88 % after 72 h of glycerol dehydration.