Bio-oil obtained from biomass can be used as an important raw material for hydrogen production. In this work, acetic acid (HAc) from bio-oil was selected as the model compound to produce hydrogen via auto-thermal reforming (ATR). Fe-promoted Co-based hydrotalcite-like Co_xAl₃Fe_yO_m±δ catalysts were prepared by co-precipitation method and characterized by XRD, N₂ physisorption, H₂-TPR and TG to study the relationship between the catalytic performance and structure within these catalysts. The characterization results show that hydrotalcite-like structure of (Co/Fe)_xAl₂CO₃(OH)_y·zH₂O were obtained by co-precipitation, then transformed to alumina supported spinel structures, including CoAl₂O₄, Co₃O₄, Fe₃O₄, and FeAl₂O₄, after calcination. BJH analysis indicated that within these calcined Co_xAl₃Fe_yO_m±δ catalysts, there were mesoporous structures, in which the Co_0.45Al₃Fe_0.4O_5.55±δ centered structure with pore size distribution 4 nm. As suggested by H₂-TPR and XRD, the reducibility of Co metal was enhanced with the Fe promoter, and there were CoFe alloys formed after reduction. In the stability test, the hydrogen yield reached 2.72 mol-H₂/mol-HAc and remained stable, meanwhile, the CoFe alloy was also stable and no carbon deposit was detected after reaction, indicating that there was high resistance to oxidation and coking within Fe-promoted Co_xAl₃Fe_yO_m±δ catalysts.