The surface structure of supports is crucial to fabricate efficient supported catalysts for water-gas shift (WGS). Here, hardly reducible ZrO2 was etched with hydrogen (H), aiming to modify surface structures with sufficient stable oxygen vacancies. After deposition of gold species, the obtained khaki ZrO2-H notably improved WGS catalytic activities and stabilities in comparison to the traditional white ZrO2. The characterization results and quantitative analysis indicate that sufficient surface oxygen vacancies of ZrO2-H support give rise to more metallic Au0 species and higher microstrain, which all boost WGS catalytic activities. Furthermore, optoelectronic properties were successfully used to correlate with their WGS thermocatalytic activities, and then a modified electron flow process was proposed to understand the WGS pathway. For one thing, the introduction of surface oxygen vacancies narrowed the band gap of ZrO2 and decreased the Ohmic barrier, which facilitated the flow of "hot-electron". For another thing, the conduction band electrons can be easily trapped by oxygen vacancies of ZrO2 supports, and then these trapped electrons immediately take part in reduction of H2O to H2. Thus, the electron recombination was suppressed and the WGS catalytic activity was improved. It is worth extending H2-etching technology to improve other thermocatalytic reactions.