The evolution of microstructure and mechanical properties of TiB2–7.5 wt% WC-based cermets sintered at different temperatures were investigated. The results showed that eutectic liquid phase appeared at around 1335 °C, indicating that solid-phase sintering occurred below that temperature, while liquid-phase sintering occurred above that temperature. TiB2, W2CoB2, WB and CoNi phases were detected in the XRD patterns of cermets sintered at different temperatures, and TEM analysis showed the presence of TiC phase. So the following chemical reaction should occur: TiB2 + WC + Co → W2CoB2 + WB + TiC. The TiB2 core - (Ti, W, Co, Ni)(B, C) rim phase were observed in the cermet sintered at 1397 °C. As the increase of sintering temperature, the solubility of WC and TiB2 in CoNi binder phase, and the number of core-rim structure hard phase particles increased. The formation of core-rim structure enhanced the interfacial bonding strength between TiB2 phase and CoNi binder, which was beneficial for improving the strength and toughness of cermets. The cermets sintered at 1465 °C had good comprehensive mechanical properties, with a relative density of 99.62%, a hardness of 17.34 ± 0.43 GPa, a transversal rupture strength of 2038 ± 53 MPa, and an indentation fracture toughness of 12.15 ± 0.32 MPa·m1/2.