Ethanol steam reforming (ESR) was considered as a promising technology that could realize high-efficiency hydrogen production from biomass resources. In this work, it utilized attapulgite (ATP) as silicon source to synthesize ATP-based MCM-41 (AM) and then manufactured AM-supported Ni/Ce/Zr catalysts (named as NixCeyZr/AM-T) by sol–gel assisted impregnation method. Meanwhile, the effects of Ce/Zr additives and calcination temperature on the structure of as-prepared catalysts were also studied. Various characterizations illustrated that the AM promoted the uniform distribution of metal oxides due to its adequate surface area and physical confinement effect that originated from ordered hexagonal mesoporous (OHM) structure. Additionally, the characterization results demonstrated that appropriate Ce-Zr simultaneous addition (2.5 wt%) and calcination temperature optimized the electronic interaction among Ni/Ce/Zr components. Amongst, the Ni2.5Ce2.5Zr/AM-600 catalyst presented the highest concentration of metallic Ni, OV and strong basic sites, attributed to the synergistic effect between physical confinement effect and optimal electronic interaction among Ni/Ce/Zr components. Therefore, the Ni2.5Ce2.5Zr/AM-600 exhibited the highest conversion of ethanol to gas product (95.0%), H2 yield (64.6%) and outstanding stability in ESR process. Furthermore, XRD, HRTEM and TG analyses confirmed that Ni2.5Ce2.5Zr/AM-600 also presented superior resistance to sintering, oxidation and carbon deposit. This paper provided a new opportunity to prepare efficient and low-cost AM-supported Ni/Ce/Zr catalysts for ESR.