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Arsenic in drinking water is one of the most concerning problems nowadays due to its high toxicity. The aim of this work is the photocatalytic oxidation of As(III) to As(V) under visible light. This study is focused on the use of gadolinium-doped bismuth ferrite as a photocatalyst active under visible light. Different gadolinium amounts were evaluated (0, 0.5, 1, 2, 5, 10 mol%), and 2 mol% resulted in the best gadolinium amount to reach higher photocatalytic efficiency in terms of As(V) production. The samples were thoroughly characterized in their optical, structural, and morphological properties. The results allowed us to identify an optimal concentration of gadolinium equal to 2 mol%. The reactive oxygen species most responsible for the photocatalytic mechanism, evaluated through the addition of radical scavengers, were O2−● and e−. Finally, a photocatalytic test was performed with a drinking water sample polluted by As(III), showing photocatalytic performance similar to distilled water. Therefore, gadolinium-doped bismuth ferrite can be considered an efficient catalytic material for the oxidation of As(III) to As(V) under visible light. [ABSTRACT FROM AUTHOR]