Summary Chemical looping steam reforming (CLSR) of acetic acid as bio‐oil model compound is a suitable way to produce hydrogen‐rich syngas. The LaNiO3 and LaNi0.8M0.2O3 (M = Fe, Co, Mn, and Cu) perovskites were prepared via the sol‐gel method. The perovskites were characterized by X‐ray diffraction (XRD), thermogravimetry (TG), and test activity of hydrogen‐rich syngas in a fixed bed. XRD and TG results showed that the coke generation on LaNi0.8Fe0.2O3 needs a lower decomposition temperature, and a stable structure was appeared after reaction. The activity order of hydrogen‐rich syngas on five types of perovskite is LaNi0.8Fe0.2O3 > LaNi0.8Co0.2O3 > LaNiO3 > LaNi0.8Mn0.2O3 > LaNi0.8Cu0.2O3 at 650°C, mole ratio of steam/carbon (2:1), and sample mixture flow (GHSV = 34 736 g of feed/(g catalyst h)). The CLSR of acetic acid with LaNi0.8Fe0.2O3 at GHSV = 43 992 g of feed/(g catalyst h) showed good stability. Correlated to experimental results, the adsorption energy of steam and acetic acid on five types of perovskite were calculated using density functional theory (DFT). The adsorption energy of steam (−0.61 eV) and acetic acid (−0.93 eV) of LaNi0.8Fe0.2O3 is maximum. This value of DFT calculation is well explained in the experimental results.