The formation of U-type hexaferrites with the composition Ba4B2Fe36O60 (B = Co, Ni, Zn) was studied. Samples were characterized by means of x-ray diffraction, electron microscopy (with energy-dispersive spectroscopy), and thermogravimetric and thermomagnetic analyses. U-hexaferrites are formed from the intermediate phases M-hexaferrite (BaFe12O19) and Y-hexaferrite (Ba2B2Fe12O22), which at the same time represent units in the U-hexaferrites’ crystal structure. The preparation of monophase U-hexaferrites was made possible by combining high-energy milling or chemical coprecipitation with a calcination at 1250–1300 °C. Structural defects, such as stacking faults, were observed in monophase samples with a high-resolution transmission electron microscope. The observed defects can be regarded as seeds for the formation of other hexaferrite phases after prolonged calcination times or higher calcination temperatures.