AbstractAcetic acid (HOAc) was selected as a bio-oil model compound for the steam reforming of bio-oil for hydrogen production. The influence of temperature and steam-to-carbon ratio (S/C) on the steam reforming of HOAc over hydrogen-type Zeolite Socony Mobil-5 (HZSM-5) and the catalyst with added Pd (Pd/HZSM-5) have been investigated in a fixed-bed reactor. Brunauer–Emmett–Teller surface area measurements, scanning electron microscopy, and transmission electron microscopy were performed to characterize the texture and structure of the catalysts. Upon addition of Pd to HZSM-5, the selectivity of the products was modified and the H2 yield was greatly increased. The hydrogen yield and potential hydrogen yield from the steam reforming of HOAc were as high as 60.2% and 87.5%, respectively, under optimized reaction conditions. Both the conversion of HOAc and the H2 yield over Pd/HZSM-5 were significantly enhanced with increasing S/C ratio and reaction temperature below 600 °C, whereas the H2 yield did not significantly increase at temperatures above 600 °C. The mechanism of HOAc decomposition on the Pd(111) surface was calculated via density functional theory. The optimal decomposition route was found to be CH3COOH* → CH3CO* → CH3* + CO*.