GCr15 bearing steel is widely used in the textile, aerospace, and other industries due to its excellent mechanical properties. However, traditional electroless Ni-B coatings can no longer meet the growing demand for a long service life under high-speed and heavy load conditions. This study focused on depositing Ni-B-Mo alloy coatings on GCr15 steel. An orthogonal experimental design was adopted to investigate the effects of the NiCl₂ and Na₂MoO₄ concentrations and deposition time on the deposition rate and surface hardness of the coatings. The results show that the Na₂MoO₄ concentration has the most significant impact on the deposition rate. An optimal concentration of 5.6 g/L improved both the deposition rate and hardness (up to 881 HV), while excessive Na₂MoO₄ (>15.6 g/L) reduced the coating adhesion and wear resistance. A deposition time of 1–2 h ensured a high deposition rate, but after 3 h, bath component depletion lowered the rate and caused coating defects. The NiCl₂ concentration (20–30 g/L) had a relatively minor influence on the deposition rate but stabilized the Ni²⁺ ion supply, enhancing the coating compactness. The optimized parameters were 5.6 g/L Na₂MoO₄, 25 g/L NiCl₂, and 2 h of deposition. The coating exhibited high hardness, strong adhesion, and excellent wear resistance. After heat treatment at 400 °C for 1 h, the coating transitioned from being amorphous to nanocrystalline, forming Ni₂B, Ni₃B, and Mo₂C phases, increasing the hardness from 737.49 HV to 916.19 HV and reducing the friction coefficient to 0.38.