A Ni-Ti-B alloy powder prepared by mechanical alloying (MA) of individual Ni, Ti, and B components is examined with the aim of elucidating the phase transitions and crystallization during heat treatment. Ti and B atoms penetrating into the Ni lattice result in a Ni (Ti, B) solid solution and an amorphous phase. Differential thermal analysis (DTA) reveals peaks related to the decomposition of the metastable Ni (Ti, B) solid solution and the separation of equilibrium Ni3Ti, TiB2, and τ-Ni20Ti3B6 phases. The exothermal effects in the DTA curves move to lower temperatures with increasing milling time. The formation of a TiB2 phase by annealing indicates that the mechanochemical reaction of the Ni-Ti-B alloy does not comply with the alloy composition in the ternary phase diagram, and Ti-B bonds are found to be more preferable than Ni-B bonds.