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For the purpose of establishing a simple route to prepare a metal-semiconductor hybrid catalyst efficiently and reduce its cost through precise doping noble metals. In this study, ultra-trace silver doped TiO2 photocatalysts were fabricated via a “green” ultrasonic impregnation-assisted photoreduction strategy in an ethanol system, and its photocatalytic performance was systematically investigated by utilizing Cr(VI) as the model contaminant. A schottky energy barrier was constructed in Ag@TiO2, which served as a recombination center and possessed superior photocatalytic activity for Cr(VI) reduction. The obtained catalysts exhibited a significant e−/h+ separation efficiency which directly led to an obvious photocatalytic property enhancement. Then, the resultant Ag@TiO2 (0.06 wt %, 30 min irradiation) showed about 2.5 times the activity as that of commercial P25 NPs for Cr(VI) degradation. Moreover, after five cycles, it still maintained considerably high catalytic ability (62%). This work provides a deep insight into preparation techniques of metal-semiconductor photocatalyst and broadens their application prospect.