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Abstract A comprehensive comparison between BiFeO3-reduced graphene oxide (rGO) nanocomposite and Bi25FeO40-rGO nanocomposite has been performed to investigate their photocatalytic abilities in degradation of Rhodamine B dye and generation of hydrogen by water-splitting. The hydrothermal technique adapted for synthesis of the nanocomposites provides a versatile temperature-controlled phase selection between perovskite BiFeO3 and sillenite Bi25FeO40. Both perovskite and sillenite structured nanocomposites are stable and exhibit considerably higher photocatalytic ability over pure BiFeO3 nanoparticles and commercially available Degussa P25 titania. Notably, Bi25FeO40-rGO nanocomposite has demonstrated superior photocatalytic ability and stability under visible light irradiation than that of BiFeO3-rGO nanocomposite. The possible mechanism behind the superior photocatalytic performance of Bi25FeO40-rGO nanocomposite has been critically discussed.