TaB2-SiC coating modified by different content of MoSi2 was fabricated on graphite substrate with SiC inner coating by liquid phase sintering to elevate the anti-oxidation capability of the TaB2-SiC coatings. As compared to the sample with the TaB2-40wt.%SiC coating, the coating sample modified with MoSi2 exhibited a weight gain trend at lower temperatures, the fastest weight loss rate went down by 76%, and the relative oxygen permeability value reduced from about 1% to near 0. More importantly, the large amount of SiO2 glass phase produced over the coating during oxidation was in contact with the modification of MoSi2, which was proved to be beneficial to the dispersion of Ta-oxides. A concomitantly formed continuous Ta-Si-O-B compound glass layer showed excellent capacity to prevent oxygen penetration. However, when the TaB2 content was sacrificed to increase the MoSi2 content, the relative oxygen permeability of the coating increased instead of decreased. Thus, on the basis of ample TaB2 content, increasing the MoSi2 content of the coating is conducive to reducing the relative oxygen permeability of the coatings in a broad temperature region.