AbstractTo understand the structure‐reactivity relationship of Ni/La2O3, and eventually get more applicable catalysts for DRM, glycine nitrate combustion (GNC), precipitation (PP) and thermal decomposition (TD) methods have been used to prepare La2O3 supports. Although all the supports possess a hexagonal La2O3 phase, their bulk and surface properties are significantly changed. By using them as supports, the interactions between NiO/Ni and La2O3 are varied, thus achieving Ni/La2O3 catalysts with different activity, stability and anti‐coking ability, which follow the order of 5Ni/La2O3‐GNC>5Ni/La2O3‐PP>5Ni/La2O3‐TD. On La2O3 having a higher surface area, a catalyst with a higher active metallic Ni surface area can be achieved. Therefore, the interfaces between Ni and La2O2CO3 can be enlarged, which effectively facilitates the reaction between carbon deposits and the La2O2CO3 formed during the DRM, thus preventing the accumulation of both and keeping the catalyst surface clean, active and stable. In addition, the amount of surface alkaline and active oxygen sites of the reduced catalysts obey the order of 5Ni/La2O3‐GNC>5Ni/La2O3‐PP>5Ni/La2O3‐TD, which is well consistent with the reaction performance. Therefore, these two factors are also believed to be critical to decide the reaction performance. It is concluded that Ni/La2O3 catalysts with high activity, stability and potent anti‐coking ability for DRM can be achieved by preparing catalysts with high Ni dispersion.