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Auto-thermal reforming (ATR) of acetic acid (HAc) is one of the potential approaches to produce hydrogen. However, the current catalysts suffered from deactivation raised from sintering and carbon deposition. In order to address these concerns, a series of Co-Al-Ba composite oxide catalysts with different Ba dopings were synthesized by Pechini method, and the activity of hydrogen production via ATR of HAc was evaluated. The CAB50 catalyst with 50 wt% of BaO presented superior activity and stability: the conversion of HAc was stable at 100%, while the hydrogen yield was maintained at 2.4 mol-H2/mol HAc. This can be attributed to the replacement of Co by Ba in CoAl2O4 spinel, hence more active species of Co0 were exposed over the stable BaAl2O4 skeleton, promoting adsorption and activation of HAc with stability. Meanwhile, the TG analysis showed that suitable amount of Ba doping promoted gasification of coking precursors and relieved carbon deposition, as also proved by the SEM. Highlights: Co-Al-O catalysts with Ba species were prepared by Pechini method. Active Co0 species were mainly obtained via reduction of BaCoO3-δ phase in CAB50 catalyst. The reducibility of cobalt-based catalyst was improved. High catalytic performance and stability were found over CAB50 catalyst. Carbon deposition was constrained with Ba species over Co-Al-Ba composite oxide catalysts. [ABSTRACT FROM AUTHOR]