The fate of arsenic in the water environment is of great concern. Here, the influences of oxalic acid and UV light illumination on the dissolution of naked ferrihydrite (Fhy), Fhy loaded with As(V) [Fhy*-As(V)], as well as the fate of As(V) at pH 3.0 were studied. With the assistance of oxalic acid, complexes of Fe(III)-oxalic acid produced on Fhy/Fhy*-As(V) were reduced to Fe(II)-oxalic acid by photo-induced electrons under UV light irradiation. UV light has nearly no impact on the release of As(V) in the system of Fhy*-As(V) without the assistance of oxalic acid. Nevertheless, in the existence of oxalic acid, UV light illumination resulted in the contents of liberated As(V) decreased by 775–1300% compared to that without light. Considering the coexistence of As(V), oxalic acid as well as iron oxides in aquatic environments, the present study revealed that UV illumination could enhance the retention of As(V) on Fhy in the acidic water environment containing oxalic acid.