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The well-dispersed Co species which partly incorporated into the lattice of CeO 2 (nanorod) was successfully synthesized, and a higher proportion of Ce3+/(Ce3+ + Ce4+) and enhanced oxygen mobility were thus obtained, which accounts for the high reactivity in auto-thermal reforming of acetic acid. [Display omitted] • Well-dispersed Co species partly doped into the lattice of CeO 2 (nanorod). • Enhanced oxygen mobility and higher Ce3+ was observed over Co-Ce-O (nanorod). • Co-Ce-O (nanorod) presents high hydrogen yield of 2.69 mol-H 2 /mol-HAc at 600 °C. As the preparation method was vital to modify the structure of catalysts, Co-Ce-O oxides were fabricated via different hydrothermal methods and evaluated in auto-thermal reforming (ATR) of acetic acid (HAc) for hydrogen production. Results of characterizations, including XRD, BET, H 2 -TPR, SEM and XPS, indicated the structure and electronic characteristics of each catalyst varied with different synthesis methods. In the case of CC-R with the morphology of nanorod, well-dispersed Co species were partly incorporated into the lattice of CeO 2 support, resulting in a higher proportion of Ce3+/(Ce3+ + Ce4+) and enhanced oxygen mobility. Consequently, it exhibited a promising catalytic performance in a 10-h testing in ATR of HAc: HAc conversion maintained at 96.8% with hydrogen yield recorded at 2.69 mol-H 2 /mol-HAc at 600 °C, while almost no by-product was detected, demonstrating its potential for hydrogen production. [ABSTRACT FROM AUTHOR]