In this paper, TiH2-47Al-5Nb (at.%) and TiH2-47Al-7Nb(at.%) alloys were mixed and synthesized using TiH2, Al and Nb powders. The composition and morphology evolution of the mixed powder were systematically investigated during high energy ball milling. The results show obvious that structure change of the particle during milling, and amorphous, TiAl, Ti3Al and Ti2Al phases at nanoscale are formed. The addition of Nb shows an active influence on the decomposition of TiH2 and formation of TiAl-intermetallics. Compare with Ti-Al system alloy, the forming process of TiAl-intermetallics for TiH2-Al-Nb system alloy is different and slower. Ti2Al metastable phase formed after ball milling for 15 h in our experiments.