In this investigation, in situ synthesis of TiB-reinforced Ti-based alloy was carried out by powder metallurgy. The Ti (TiH2)—Al and B powders were ball milled for 40 h to obtain a mixed powder with a nominal composition of Ti-7Al-0.2B (wt. %) and TiH2-7Al-0.2B (wt. %). After milling the mixed powder by using a vacuum hot pressing sintering furnace (1200 °C sintering temperature, 30 MPa pressure, 1 h holding pressure), TiB-reinforced Ti-based alloy was prepared in situ. The compression tests were carried out on a WDW-200 universal testing machine at 550 °C, 600 °C, and 650 °C, and at the strain rates of 1 × 10−4 s−1, 3 × 10−4 s−1, and 5 × 10−4 s−1 to investigate the alloy compression and rheological behavior of the prepared alloy. It was observed that Ti-7Al-0.2B and TiH2-7Al-0.2B alloy formed a TiB phase and α-Ti duplex structure after low-energy ball milling and hot pressed sintering. This is because the in situ synthesis of TiB fiber reinforced phase hinders grain boundary migration and grain growth. Therefore, the TiB phase in Ti-7Al-0.2B alloy is fine, evenly distributed and effective in suppressing grain growth. Alloy materials are heat sensitive and strain-rate sensitive alloys, and the peaks of high-temperature compressive stress decrease with the decrease of the strain rate and the increase of the temperature. At the same temperature and rate conditions, the highest peak flow stress of TiH2-7Al-0.2B is slightly higher than that of Ti-7Al-0.2B. In the ball milling and sintering process of TiH2-7Al-0.2B alloy, the decomposition of H from TiH2 cleanses the surface of Ti particles. This leads to the reduction of the possibility of contamination, and also has a good effect in improving the compression performance.