In this work, a synthesis route of Ni3B, an attractive material for making heating elements and a promising component for catalysts, was developed using high-energy ball milling of nickel and boron powder mixtures. The milling duration was varied from 1 to 15 min. Ball milling led to partial dissolution of boron in the crystalline lattice of nickel and crystallite size refinement of nickel. Heating of the ball-milled mixtures at a constant rate led to thermal explosion, the indications of which were a rapid temperature rise and the formation of boride phases. The duration of ball milling was shown to influence the phase composition of the products of thermal explosion. The time of milling ensuring the formation of single-phase Ni3B was determined to be 7 min. The ignition temperature of thermal explosion decreased with the milling time: a decrease by more than 300 °C was observed for the mixture milled for 15 min relative to the non-milled mixture. The maximum temperature developed during thermal explosion increased in the mixture milled for 1 min relative to the non-milled mixture and then decreased with the milling time reaching the level of the non-milled mixture after 15 min of milling. The observed dependence of the maximum temperature on the milling time is related to the net effect of mixing uniformity improvement between the reactants and a partial transformation of the reaction mixtures into Ni(B) solid solutions and Ni3B during milling. The proposed synthesis route of a single-phase Ni3B powder has advantages of short processing time and low-energy consumption.