The ZrB2–BN composite without ZrC impurity was prepared successfully using reactive hot pressing via carbothermal reduction of ZrO2 with B4C, C, and BN powders. The influences of additives and sintering temperature on the phase and microstructure of composites were investigated. The formation reaction of ZrC was inhibited by decreasing the evaporation of intermediate product B2O3 due to forming a SiO2–B2O3 eutectic system with the addition of SiO2 or SiO2–CaF2. In comparison, SiO2–CaF2 exhibited better inhibition capacity of ZrC. ZrB2–BN composite without impure ZrC phase was achieved. In addition, the content of ZrO2 decreased with increasing sintering temperature, and finally disappeared when sintered at 1800°C. Moreover, the relative density of the ZrB2–BN composite reached 96.9%.