Effects of Mo addition on the microstructure, mechanical properties, and abrasive wear properties of an oriented bulk Fe2B crystal have been investigated systematically in the present paper. Five groups of pure Fe2B samples with different Mo contents have been examined by optical microscope, X-ray diffraction, scanning electron microscope integrated with energy disperse spectroscopy, microhardness tester, and three-point bending testing of fracture toughness. The results indicate that Mo tends to segregate on the grain boundaries after doping; with increasing Mo addition, interplanar spacing of the (002) crystal plane of Fe2B decreases firstly and then increases slightly while that of (200) increases gradually; microhardness on the transversal section changes little while that on the longitudinal section increases firstly and then decreases [possessing the opposite trend to interplanar spacing of (002)]; fracture toughness and wear resistance of both transversal and longitudinal samples can be improved to some extent with Mo addition less than 2.0 wt%. In conclusion, appropriate Mo addition plays a positive role in the improvement of mechanical properties of oriented bulk Fe2B.