To evaluate the effect of boride reinforcement on the microstructure and wear resistance of nickel-based coatings, NiCr-MoB2 coatings with varying MoB2 contents were prepared by atmospheric plasma spraying. MoB2 particles are deposited without structural rearrangement, enhancing the microhardness through dispersion strengthening. The hardness of NiCr-15 wt.%MoB2 (NM15) coating reached a maximum value of 406.53 HV0.1. Phase analysis revealed that a small amount of light atoms is involved in the formation of intermetallic compounds, increasing the material’s resistance to plastic deformation. As the content of MoB2 increases, the shock effect causes the porosity of the coating to decrease and eventually stabilize at 2-3%. Friction experiments show that the adhesion of Ni-based coatings is suppressed after introducing reinforcing phases. The friction coefficient and wear rate exhibit consistent trends. NiCr-10 wt.%MoB2 (NM10) exhibits the optimum tribological performance, attaining a minimum wear rate of 3.85 × 10−6 mm3/N·m. The oxide film dynamically formed on the sliding surface prevents further damage to the internal materials of the coating. The wear mechanism of coatings is influenced by the synergistic effects of hardness and toughness, and it involves a combination of adhesive, oxidative, and abrasive wear. However, excessive addition of MoB2 accelerates brittle crack propagation and exacerbates material loss.