AbstractZirconium boride (ZrB2) whiskers hold significant potential for toughening ultra‐high temperature ceramics (UHTCs). Yet, their fabrication remains challenging due to limited knowledge of the microstructure evolution. Herein, high‐purity ZrB2 whiskers were successfully prepared by electrospinning combined with carbothermal reduction. Specifically, a precursor solution containing Zr–O–C–B networks stabilized through hydrogen bonds with polyvinyl pyrrolidone was synthesized as a spinnable ZrB2 precursor. High‐purity ZrB2 whiskers with a diameter of ca. 200 nm and a length of 5–10 µm were obtained by precise heat treatment of ZrB2 precursor fibers. In this process, ZrO2 grains formed initially and transformed into ZrB2 grains through carbothermal reduction, which further converted into ZrB2 whiskers through a solid‐liquid‐solid mechanism. To testify to the toughening effect for UHTCs, the ZrB2 whiskers were added into ZrB2 powders and followed by sintering. This strategic addition of 5 wt% ZrB2 whiskers led to a 19% enhancement in the fracture toughness of ZrB2 bulk. This study illuminated the preparation strategy and formation mechanism for ZrB2 whiskers and their application for toughening UHTCs.