The UFeB4 phase present in different alloys of the B–Fe–U system was studied by powder X-ray diffraction (PXRD) and scanning electron microscopy complemented with energy-dispersive spectroscopy and electron backscattered diffraction (EBSD). The PXRD data showed that the ternary compound crystallized adopting essentially the YCrB4-type structure. However, microstructural observations revealed that under high undercooling conditions the UFeB4 phase exhibits a random distribution of defects parallel to, which are consistently associated with intense higher-order Laue zone rings in EBSD patterns. Indexation of the EBSD patterns showed that the defective structure is compatible with an intergrowth of YCrB4- and ThMoB4-type layers according to the (010)YCrB4
orientation relation previously reported for an analogous compound. Magnetic studies indicated that the annealed UFeB4 compound has a paramagnetic behavior in the 2–300 K temperature range.