Sustainable　synthesis　of　acrolein,　a　key　chemical　intermediate,　from　biomass-derived　glycerol　is　highly　attractive.　However,　conventional　catalysts　for　the　dehydration　of　glycerol　suffer　from　low　acrolein　selectivity　and　high　deactivation　tendency.　Herein,　a　novel　green　catalyst　(HPW/T-0.6　S-COOH)　was　prepared　and　employed　in　the　dehydration　of　glycerol　in　a　continuous　flow　reactor.　The　performance　of　different　catalysts　and　the　effects　of　reaction　conditions　(reaction　temperature,　N-2　flow　rate,　and　glycerol　concentration)　were　examined.　The　HPW/T-0.6　S-COOH　catalyst　provides　the　best　glycerol　conversion　of　96.38%　and　acrolein　selectivity　of　92.01%.　The　NH3-TPD　and　pyridine-FTIR　results　indicate　that　the　Bronsted　acid　site　is　more　susceptible　to　acrolein,　while　the　weak　strength　acid　site　effectively　prevents　the　further　reaction　of　acrolein,　providing　practical　insights　for　the　rational　design　of　efficient　and　continuous　synthesis　of　acrolein　catalysts.