Methanol　steam　reforming　faces　a　significant　challenge　due　to　CO　formation,　which　can　lead　to　poisoning　of　fuel　cell　electrodes.　This　study　introduces　a　series　of　Pd/ZnO　catalysts　prepared　by　ethylene　glycol　reduction,　exhibiting　remarkable　selectivity　in　methanol　steam　reforming　(MSR).　The　majority　of　palladium　species　exist　in　the　form　of　PdZn　alloy,　attributed　to　the　dual　reduction　process.　This　process,　along　with　the　generation　of　zinc　vacancies　and　oxygen　vacancies,　enhances　the　interaction　between　the　metal-carrier,　promoting　the　formation　of　PdZn　alloy,　significantly　improving　CO2　selectivity　and　catalytic　activity.　Even　at　a　high　temperature　of　400　°C,　the　active　phase　remains　stable.　After　5　hours　of　MSR,　the　3%　Pd/ZnO-300　H2　catalyst　achieves　a　hydrogen　production　rate　of　1628.0　mmol·gcat−1·h−1,　with　methanol　conversion　stabilized　at　94%,　CO2　selectivity　reaching　97.7%,　and　CO　content　as　low　as　0.5%.　These　results　outperform　recent　studies　on　hydrogen　production.　Furthermore,　DFT　calculations　elucidate　the　complete　reaction　pathway　(111)　on　PdZn.　This　study　provides　initial　insights　into　the　influence　of　metal-carrier　interaction　on　the　formation　of　PdZn　alloy,　suggesting　a　new　direction　for　palladium-based　catalysts　in　methanol　steam　reforming.　©　2024　Elsevier　B.V.