The microstructure of oxidative layer of MoSi2 at 1200-1600 degreesC was investigated by SEM, TEM and XRD. The surface layer consists of the mixture of SiO2 and other oxides under 1240 degreesC, which has low compactness. There is needlelike, flabelliform or penniform low temperature quartz in the surface layer at 1240-1520 degreesC, and the layer is thin. Above 1520 degreesC the oxidative layer contains mass-like, granular-like or honeycomb cristobalite and is compact, thick and homogeneous, so the oxidate resistance of MoSi2 is enhanced obviously.