Ti₂AlNb-based alloys, as emerging lightweight high-temperature structural materials, have shown great potential for aerospace applications owing to their outstanding creep resistance, strong plasticity, and impressive high-temperature oxidation resistance. However, the material has yet to see widespread use owing to its poor formability and processability. Compared to traditional melting and forging methods, powder metallurgy has proven to be an effective method for preparing this alloy with a required shape, thereby circumventing phase transformation during hot working. The properties of Ti₂AlNb-based alloy can be enhanced by adding stabilized elements to the B2 or α₂ phase. Among these metallic elements, V has been demonstrated to effectively increase the ductility and high-temperature strength of Ti₂AlNb-based alloys. However, the mechanism of the V addition's effect on the microstructure and properties of Ti₂AlNb-based alloys during aging treatment has not been systematically clarified. Therefore, investigating the influence of powder sintering and post-heat treatment on the microstructure and properties of Ti-22Al-25Nb-1V alloys is crucial for accelerating their industrialization process. This investigation forms the basis of this work. A detailed study on the role of V in the microstructure and deformation responses of the Ti₂AlNb alloy was performed. This involved preparing V-added and V-free Ti-22Al-25Nb alloys via spark plasma sintering. Then, the sintered alloys were solution treated at 1300 ^oC for 4 h and subsequently aged at temperatures from 800 ^oC to 1050 ^oC for 2 h for microstructure modification. The detailed microstructure of the alloys was analyzed using X-ray diffraction and electron microscopy. The results revealed that by adding V, the volume fraction of the residual α₂ phase improves. The microhardness of the V-doped alloys is significantly enhanced compared to the undoped alloys and reached a maximum value of 503 HV at an aging temperature of 850 ^oC. This α₂ phase pins the grain boundary during heat treatment, resulting in an alloy with a refined grain size. Additionally, V additions can inhibit the B2 + α₂ → O transition, promoting a finer O/α₂ phase precipitate and higher hardness. Furthermore, microstructural analysis proved that the segregation of V and Nb in the B2 phase will cause the “curved” structure, including Nb- and V-rich B2 and Nb- and V-lean α₂ phases. The partial replacement of Nb by V reduced the lattice parameter in the B2 phase, which further improves the hardness of this alloy.