Catalyst sintering caused by high temperature operating conditions during ethanol steam reforming (ESR) is a common issue for traditional catalysts with low Tammann temperature metals. In recent years, high entropy oxides have been popular in thermal catalysis due to their special thermodynamics and kinetics characteristics, which is expected to be a suitable approach for enhancing catalyst stability. This paper first reports the application of HEO in ESR and the characterization. The results exhibited a nano structure (CoCrFeNiAl)₃O₄ HEO with a spinel-phase and was successfully synthesized by a polyol hydrothermal precipitation-calcination method. An abundance of oxygen vacancies were formed, and were further enriched in a hydrogen atmosphere as the M–O bond opened. Interestingly, its self-reorganization featured the rendered the metals spilling out of the HEO bulk phase as active species for hydrogen production during ESR, whereas the isolated metal cation randomly dissolved into the parent metal oxide cell again after the reaction instead of agglomerating over the catalyst surface. This gave the (CoCrFeNiAl)₃O₄ a large number of dispersed active sites, as well as a high thermal stability. In addition, 81% of the hydrogen yield as well as 85% of H₂ selectivity were achieved at 600 °C. This research might offer possibilities for the development of thermal catalytic hydrogen production under high temperature conditions such as steam reforming.