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Oxide‐based photoelectrodes for solar water splitting have gained growing attention because of their decent stability and cost‐effectiveness. Particularly, α‐SnWO4 has been regarded as a potential next‐generation light absorbing material due to the predicted favorable bandgap of 1.9 eV. Herein, the investigation and amelioration of the crystallinity as a performance dominating factor to the α‐SnWO4‐based photoanode are demonstrated. The improvement is attributed to a unique crystallization process induced by the formation of oxygen vacancies in the reductive atmosphere at 500 °C. The sample exhibits notably enhanced visible‐light absorption and an improved charge transport property. Electrochemical measurements reveal a cathodic shift of the flat‐band potential, corresponding to the impacted band position. The photocurrent is enhanced from 0.03 to 0.42 mA cm−2 (AM1.5, 1.23 VRHE). Such a new treatment can be used as an effective tool for developing α‐SnWO4 into efficient photoelectrocatalytic (PEC) materials.