The influence of partial substitution of Hf for Zr on the microstructure and thermal stability of near‐α high‐temperature titanium alloys is systematically investigated. The results show that the addition of Hf promotes the refinement of precipitated phases of the silicides and α2 phase and the (Ti,Zr,Hf)6(Si,Sn)3 S2‐type silicides were formed in alloys after aging treatment. During thermal exposure, both silicides and α2 phase in alloy with 2.5 wt% Hf exhibited excellent anti‐coarsening ability, which may be attributed to the slow diffusion of Hf in Ti that significantly inhibited the growth rate of the precipitated phase. The loss of plasticity of near‐α titanium alloys after thermal exposure is mainly due to the precipitation and coarsening of silicides and α2 phase, therefore, the Hf‐containing titanium alloy has more excellent thermal stability, i.e., the plasticity loss rate is decreased from 34.8% (the alloy without Hf) to 7.4% (the alloy with 2.5 wt% Hf).