In this work, single-phase ferroelectric (FE) and ferromagnetic (FM) layer-structured semiconductive Aurivillius Bi₇Fe₃Ti₃O₂₁ nanoshelves with a direct band gap of ∼2.22 eV were controllably synthesized by a facile hydrothermal method. The nanoshelf structure could suppress the unwanted aggregation problem introduced by spontaneous polarization and ensure a high Brunauer–Emmett–Teller surface area. The Bi₇Fe₃Ti₃O₂₁ nanoshelves with co-existing FE and FM properties were demonstrated as visible-light-driven photocatalysts for decomposing Rhodamine B. This finding may open a window for developing new visible-light-driven photocatalysts because the used layer-structured Aurivillius phase has significant potential in elemental doping and further structural engineering applications.