The effect of ZrO2 addition on sintering behavior and mechanical properties of both hot-pressed and pressureless-sintered B4C was investigated. The addition of ZrO2 improved the densification behavior of B4C remarkably via a reaction with the B4C to form ZrB2 at elevated temperatures. When B4C was densified at 2000 °C by hot pressing, only a small amount (approximately 2.5 vol%) of ZrO2 was necessary to achieve a full densification. Excellent mechanical properties (hardness, elastic modulus, flexural strength, and fracture toughness) were observed in those specimens. As the amount of ZrO2 was increased further, the mechanical properties were reduced, except for the fracture toughness, apparently due to the formation of too much ZrB2 in the specimen. Without the applied pressure, larger amounts of ZrO2 should be added to obtain a body with high relative density. When the B4C was sintered at 2175 °C with addition of 10 vol% ZrO2, the specimen has a density higher than 95% of the theoretical, and hardness and flexural strength of 25 GPa and 400 MPa, respectively.