ZrB2-SiC ultra-high temperature ceramics (UHTCs) were pressureless sintered with Y2O3-Al2O3 as the sintering additives. The effects of sintering additive and crystallization annealing on the microstructure and properties of ZrB2-SiC UHTCs were investigated. Sintering was activated by producing liquid phase of Y2O3 and Al2O3. The relative density of sintered ZrB2-20wt%SiC ceramic could reach 96% when the content of sintering additive was 6% and the sintering temperature was 1750°C and its bending strength, Vickers hardness, and fracture toughness were 412 MPa, 13 GPa, and 6.0 MPa•m1/2, respectively. The crystallization annealing can result in YAG phase from grain boundary and enhance the high temperature properties of the UHTCs. The UHTCs have excellent ablation resistance at ultra-high temperatures, and a very low ablation rate of 0.0006 mm/s after ablation for 900s at 2800°C.