The present work reports on the preparation of the Ta5SiB2 compound by highenergy ball milling and subsequent heat treatment from elemental Ta-12.5at%Si-25at%B powder mixture. The milling process was carried out at room temperature in a planetary ball mill under argon atmosphere. Following the milling process, the powders were heat-treated at 1200oC for 4h under Ar atmosphere in order to obtain the equilibrium microstructure. The milled and heat-treated powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results indicated that the Si peaks disappeared after milling for 1h. It was noted that the broadening and the reduced intensity of Ta peaks occurred continuously up to milling for 10h, suggesting that the Si and B atoms were preferentially dissolved into the Ta lattice during ball milling to form a supersaturated solid solution. A halo was formed in Ta-12.5at%Si-25at%B powders milled for 100h, suggesting that an amorphous phase was achieved. No intermetallic phase was formed in powders milled for 200h. A large amount of Ta5SiB2 was formed after heat treatment at 1200oC for 4h. In addition, peaks of TaB and another unknown phase were also identified.