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Fabrication of low-cost and high-efficiency catalysts with excellent durability is essential to promote hydrogen production from the hydrolysis of ammonia borane (AB). Herein, we report a considerable performance improvement in hydrogen production from AB hydrolysis using Pd precursor reduction-induced morphology and vacancy engineering via in situdriving Co3O4particles to nanosheets with abundant oxygen vacancies. The achieved Pd/Co3O4–SB catalyst exhibits excellent catalytic performances for room-temperature AB hydrolysis with recorded turnover frequencies of 781/12 674 min−1in aqueous/alkali solutions. Most importantly, this catalyst shows unprecedented durability with highly maintained activity after the 20th cycle. The precursor reduction-induced morphology and oxygen vacancy modulation of the catalyst allows an abundance of catalytic active surfaces and promoted electron/mass transfer, facilitating the oxidative cleavage of the O–H bonds in attacked H2O, thereby, considerably boosting the hydrogen production through AB hydrolysis. This study presents a simple strategy to construct an effective and durable catalyst for hydrogen production from AB hydrolysis.