AbstractResearchers have demonstrated that BiFeO₃ exhibits ferroelectric hysteresis but none have shown a strong ferromagnetic response in either bulk or thin film without significant structural or compositional modification. When remanent magnetisations are observed in BiFeO₃ based thin films, iron oxide second phases are often detected. Using aberration-corrected scanning transmission electron microscopy, atomic resolution electron energy loss spectrum-mapping and quantitative energy dispersive X-ray spectroscopy analysis, we reveal the existence of a new Fe₂O₃-rich perovskite nanophase, with an approximate formula (Fe_0.6Bi_0.25Nd_0.15)³⁺ Fe³⁺O₃, formed within epitaxial Ti and Nd doped BiFeO₃ perovskite films grown by pulsed laser deposition. The incorporation of Nd and Bi ions on the A-site and coherent growth with the matrix stabilise the Fe₂O₃-rich perovskite phase and preliminary density functional theory calculations suggest that it should have a ferrimagnetic response. Perovskite-structured Fe₂O₃ has been reported previously but never conclusively proven when fabricated at high-pressure high-temperature. This work suggests the incorporation of large A-site species may help stabilise perovskite-structured Fe₂O₃. This finding is therefore significant not only to the thin film but also to the high-pressure community.