The concentration of Si plays a crucial role in the ductile‐brittle transition of Nb solid solution (NbSS) alloys, and an appropriate annealing treatment contributes to controlling the Si concentration in NbSS alloy. In this paper, Nb–1Si (at%) alloy is arc‐melted and annealed at different temperature (1300, 1400, and 1500 °C) for 10 h. After annealing, both the strength and ductility increase. Particularly, after annealing at 1300 °C, the fracture feature transforms from cleavage to dimples, and the alloy possesses good strength and retains decent ductility due to the low Si concentration and small‐sized intragranular Nb3Si particles precipitating in the NbSS. The significant effect of annealing on the fracture mechanism of Nb–1Si provides guidance for the design of Nb–Si based alloys.