Titanium silicide (Ti5Si3) and its composites show promise for applications at temperatures higher than 1000 °C. Dense Ti5Si3 was processed by reaction hot pressing of a TiH2/Si powder mixture, which involved decomposition of TiH2 into Ti and H2 at around 800 °C, a chemical reaction between Ti and liquid Si at 1500 °C forming Ti5Si3 in situ, and densification under pressure. The use of fine TiH2 particles led to the formation of a relatively fine-grained microstructure with fewer microcracks and higher hardness and fracture toughness values than those expected for a coarse-grained Ti5Si3. The addition of 8 wt pct Al as an alloying element led to the formation of Al0.67Si0.08Ti0.25 and Al2O3 in situ and a solid solution of Al in Ti5Si3. Both alloying with Al and the addition of TiC as a reinforcement phase improved the room-temperature fracture toughness. Fracture toughness measurements were performed by three-point bend testing of single-edge notch bend (SENB) specimens, as well as by indentation techniques using different models, and the data have been compared. The role of different operating toughening mechanisms such as crack deflection, bridging, branching, and energy dissipation through microcracracking have been examined. The investigation has also shown that Ti5Si3 maintains a high yield strength value up to 1200 °C.