Fe–B wear-resistant alloys often exhibit brittleness and suboptimal wear resistance, making them unsuitable for severe operational conditions. In this study, we incorporated ferromanganese powder and ferrovanadium powder were compounded into the Fe–B wear-resistant alloy by plasma cladding technology. The results indicate that the addition of a minor percentage of vanadium, such as about 2 wt%, does not induce any changes in the phase composition. The alloy layer primarily consists of (Mn,Fe)2B and γ-Fe, with vanadium predominantly dissolving in the primary (Mn,Fe)2B phase. This dissolution enhances the toughness of the hard phase and refines the grain structure. At around 4 wt% vanadium, a spherical VB phase precipitates. This inclusion elevates the impact toughness of the alloy layer. The impact toughness of the high manganese content with 4.69 wt% vanadium is the highest, up to 39.11 J/cm2, which is about 30 %higher than that of the sample without vanadium. As vanadium content rises, both the hardness and wear resistance of the alloy layer improve. The most optimal performance was observed with a manganese content of 20.15 wt% and vanadium at 4.69 wt%, achieving a hardness of 65.5 HRC and wear amounts of 48.1 mg (24 N load) and 85.0 mg (48 N load).