This work discusses on the effect of milling parameters on the TiB and TiB2 formation in Ti-50at%B and Ti-66at%B powders, respectively. Both powder mixtures were processed in a planetary ball Fritsch P-5 ball mill under Ar atmosphere, varying the milling parameters: rotary speed (150 and 200 rpm), size of balls (10 and 19mm diameter) and ball-to-powder weight ratio (2:1 and 10:1). In order to obtain the equilibrium structures the milled powders were heated at 1200oC for 1h. Samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermal analysis (DSC). XRD results indicated that extended Ti(B) solid solutions were formed during ball milling of Ti-50at%B and Ti-66at%B powders. After milling for 170h it was noted the TiB and TiB2 formation in Ti-50B and Ti-66B powders processed under higher-energy condition. DSC analysis revealed that the TiB2 formation was completed during heating of mechanically alloyed Ti-66at%B powders only. After heating at 1200oC for 1h, a large amount of TiB and TiB2 was found in Ti-B powders milled under higher energy condition.