The present study investigates the electrically activated reactive synthesis (EARS) and post-reaction electro-annealing of 3Ni-Al powder compacts. The effect of initial relative green density on EARS processing and on the microstructure and phases produced was investigated. Post-reaction electro-annealing was also conducted to investigate its effects on phase transformations and consolidation. The initial reaction resulted in the formation of Ni3Al as the major phase, with 3R martensite also being formed. The investigated variation in relative green density was found to have limited effect on the product porosity and microstructure. Post-reaction electro-annealing, however, resulted in harder products with unique microstructures, particularly the formation of Ni4.22Al0.9 in very high amounts.