Porous TiAl₃ intermetallics were fabricated through vacuum reactive sintering from Ti–75Al at.% elemental powder mixture. The phase compositions, expansion behaviors, pore characteristics and microstructure evolution of TiAl₃ intermetallics were investigated, and the pore formation mechanism was also proposed. It was found that the actual temperature of compacts showed an acute climb from 668 to 1244 °C in 166s, while the furnace temperature maintained the linear growth of 5 °C/min, which indicated that an obvious thermal explosion (TE) reaction occurred during sintering, and only single-phase TiAl₃ intermetallic was synthesized in TE products. The open porosity increased from 22.2 (green compact) to 32.8% after reactive diffusion sintering at 600 °C and rised to 58.7% after TE, then decreased to 51.2% after high-temperature homogenization at 1100 °C. Therefore, TE reaction is the dominated pore formation mechanism of porous TiAl₃ intermetallics. The pore evolution in porous TiAl₃ intermetallics occurred by the following mechanisms: certain intergranular pores remained among powder particles of green compact, then low-temperature sintering resulted in a further increase in porosity due to the Kirkendall effect. Moreover, TE reaction gave rise to a dramatic volume expansion because of the rapid increase in temperature, and high-temperature sintering caused densification and a slight shrinkage.