This study investigated the effect of Si addition on the microstructure and the silicide precipitation behavior in a novel near-β titanium alloy. The results show that coarse and continuous silicides were preferentially precipitated at the grain boundary during the solidification process, and the β grain size of the as-cast alloy was refined. Dynamic recrystallization occurs under isothermal compression, and the silicide could inhibit the growth of recrystallized grains. The element redistribution and dislocation accumulation during hot deformation promote the dynamic precipitation of silicide, resulting in a discontinuous distribution of silicides at the grain boundaries. This work provides insight into how silicide dynamic precipitation will affect the microstructure and plastic deformation behavior of metal alloys.