The in situ formation of TiB2 particulates via an interface reaction between Ti and FeB powders was studied. The effects of mechanical activation by high-energy milling on the decomposition of TiH2 and the interface reactions between Ti and FeB powders to form TiB2 were investigated. Powder mixtures were fabricated using planetary ball-milling under various milling conditions. The specific ball-milling energy was calculated from the measured electrical power consumption during milling process. High specific milling energy (152.6 kJ/g) resulted in a size reduction and homogeneous dispersion of constituent powders. This resulted in a decrease in the decomposition temperature of TiH2 and an increase in the formation reaction of TiB2 particulates in the Fe matrix, resulting in a homogeneous microstructure of nanoscale TiB2 evenly distributed within the Fe matrix. In contrast, the powder mixture milled with low specific milling energy (36.5 kJ/g) showed an inhomogeneous microstructure composed of relatively large Fe-Fe2B particles surrounded by a thin layer of Fe-TiB2 within a finely dispersed Fe-TiB2 matrix region.