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Autothermal reforming (ATR) of acetic acid (HOAc) is a promising and alternative route for hydrogen production from renewable resources, but catalyst deactivation caused by cobalt metal sintering and coking is a major concern in ATR. In this work, perovskite‐like catalysts of the formula SrxTi1–xCoO3±δ (x = 0, 0.2, 0.5, and 0.8) were prepared by evaporation‐induced self‐assembly and then evaluated in ATR for hydrogen production. The SrxTi1–xCoO3±δ catalysts exhibited high activity and stability as well as 100 % conversion of HOAc. Additionally, the Co particles with strong metal‐support interaction of SrTi(Co)O3 inhibited coking and agglomeration, and showed potential for hydrogen production by the ATR process.