Abstract Simultaneous occurrence of large ferroelectricity and strong ferromagnetism have been observed in barium hexaferrite ceramics. Barium hexaferrite (BaFe12O19) powders with hexagonal crystal structure were successfully synthesized in a polymer precursor method using barium acetate and ferric acetylacetonate as the precursors. The powders were pressed into pellets which were sintered into ceramics at 1200°C and 1300°C for 1h. The structure and morphology of the ceramics were examined using X-ray diffraction and field emission scanning electron microscopy. Large spontaneous polarization was observed in the BaFe12O19 ceramics at room temperature, revealing a clear ferroelectric hysteresis loop. The maximum remanent polarization of the BaFe12O19 ceramic was estimated approximately 11.8μCcm−2. The FeO6 octahedron in its perovskite-like hexagonal unit cell and the shift of Fe3+ off the center of octahedron are suggested to be the origin of the polarization in BaFe12O19. The BaFe12O19 ceramics also showed strong ferromagnetism at room temperature.