Photocatalytic water splitting on semiconductor photocatalysts is one of the most important physichemical processes, but its surface reaction mechanisms are not fully understood. Based upon the ATR-FTIR investigations combining with the mass spectroscopy (MS) analysis, a direct hydroxyl radical formation mechanism that is different from those observed for other semiconductor photocatalysts is proposed. This study provides the insight into overall water splitting mechanism on Ga2O3-based photocatalysts at a molecular level, and it helps one to further understand the photocatalysis on semiconductor photocatalysts.