The three-phase region of Mo₃Si-Mo₅Si₃-Mo₅SiB₂(MoSiB) exhibits excellent high-temperature oxidation resistance and is considered a highly promising high-temperature structural material. However, the presence of porous structures significantly increases the surface area exposed to oxidation. Metallic porous materials often suffer from inadequate corrosion resistance and insufficient high-temperature oxidation resistance, whereas ceramic porous materials are plagued by high brittleness. Intermetallic compounds offer a combination of the advantages of both metals and ceramics. Nevertheless, the high-temperature oxidation behavior of porous MoSiB has not yet been systematically elucidated. The study systematically investigates the effect of pore structure on the high-temperature oxidation behavior of porous MoSiB at 1000 °C and 1300 °C, with a focus on oxidation kinetics, phase evolution, surface and cross-sectional morphology and underlying oxidation mechanisms. The effects of porosity and temperature on the oxidation process are also analyzed. The results indicate that at 1000 °C, the material exhibits uniform oxidation, with lower porosity contributing to better oxidation resistance. At 1300 °C, oxidation is limited to the surface layer, where low-viscosity SiO₂(B) rapidly seals the pores to form a dense protective layer. This research reveals the high-temperature oxidation mechanism and phase evolution of porous MoSiB, providing a theoretical foundation for its application in high-temperature structural fields.