Spent MoSi₂ and MoB were used as raw materials to prepare multilayer MoSi₂/MoB coating on molybdenum by the two‐step method of Slurry Deposition and Spark Plasma Sintering. The results showed dense MoSi₂/MoB coating after sintering while penetrated cracks appeared in MoSi₂ coating due to CTE mismatch between the Mo substrate and coating. After the sintering of MoSi₂/MoB coatings, MoB and Mo₂B diffusion layers was formed between MoB transition layer and Mo substrate without defects, exhibiting good metallurgical bonding. The high‐temperature oxidation behavior of coatings (1500 °C) was also explored. After oxidation of 50 h at 1500 °C, lowest mass gain (0.035 mg/cm²) was obtained for MoSi₂/MoB coating and the oxide scale was dense and complete without voids, making the oxygen diffusion at elevated temperature inhibited. Compared with MoSi₂ coating under the same oxidation conditions, relatively thinner silica oxide scale was acquired by MoSi₂/MoB coating because of the reduction of cracks, and the multilayer coating exhibits better anti‐oxidation properties at high temperature.