Abstract: ZrB₂ powders were synthesized via a borothermal reduction reaction of ZrO₂ with the assistance of NaCl under a flowing Ar atmosphere. The optimal temperature and reaction time were 1223 K and 3 h, respectively. Compared with the reactions conducted without the addition of NaCl, those performed with the addition of an appropriate amount of NaCl finished at substantially lower temperatures. However, the addition of too much NaCl suppressed this effect. With the assistance of NaCl, a special morphology of polyhedral ZrB₂ particles covered with ZrB₂ nanosheets was obtained. Moreover, the experimental results revealed that the special morphology was the result of the combined effects of B₂O₃ and NaCl. The formation of the special microstructure is explained on the basis of the "dissolution-recrystallization" mechanism.