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Effect of Al2O3 nanoparticles (80 nm) on the grain structure and phase formation in Ni-50Ti system during high-energy mechanical alloying (MA) was studied. While the formation of NiTi B2 phase occurs progressively during MA, it is shown that the hard inclusions cause abrupt phase formation at short milling times, particularly at higher nano-Al2O3 contents. High-resolution transmission electron microscopy showed significant grain refinement in the presence of alumina nanoparticles to sizes less than 10 nm, which precedes the formation of semicrystalline structure and reduces the diffusion length and thus accelerates the phase formation. The composite powder reached steady-state MA condition at shorter milling times with finer grain structure and higher hardness.