Microstructure of the hot-pressed ZrB2 with MoSi2 additive was investigated by transmission electron microscopy (TEM). The effect of MoSi2 addition on the microstructure of the ceramic was assessed. For the pure ZrB2, the microstructure consisted of the equiaxed ZrB2 grains and a few elongated ZrB2 grains. For the ZrB2 with MoSi2 additive, the microstructure consisted almost entirely of equiaxed ZrB2 grains. A few dislocations were present in the ZrB2 grains. In addition, high-resolution TEM observations showed that the intergranular amorphous phase was absent at two ZrB2 grain boundaries in the ZrB2 with MoSi2 additive.