In this work, Ni-Al-Ti-B composite powders with Ni: Al: Ti: B atom ratio of 5.7: 1.9:1:1 were prepared by using mechanical activation (MA) method. The MA processes were performed by vibration ball mill in a water-cooled chamber for 30 h. The ball-to-powder weight ratio was 10:1. In order to reduce the oxidation of the powders during milling process, ball milling was performed under an Argon atmosphere. The evolution of morphology and microstructure of Ni-Al-Ti-B composite powders were examined at different milling stages using scanning electron microscope and X-ray diffraction. Distribution of powders size was analyzed and the results showed that there were three stages for the change of powders size: (1) at the first stage, powders size increased due to more welding than fracture of the powders within 2h of MA, (2) at the second stage, particle size continuously decreased until 16h of MA due to more fracturing than welding, and (3) after 16h of MA, the particle size remained constant when welding and fracture reached an equilibrium. Calculation results according to Scherrer equation from X-ray pattern showed that the effective grain size continuously decreased with MA time. X-ray diffraction pattern confirmed that the formation of Ni and Ti solid solution during MA process of the Ni-Al-Ti-B composite powders.