Lithium orthosilicate (Li4SiO4) is regarded as a candidate for tritium breeding in fusion reactors. In this study, the Li4SiO4-Li2ZrO3 biphasic was developed to improve the sinterability, density, and mechanical properties of Li4SiO4. The Li4SiO4-xLi2ZrO3 (x = 0.5, 1) composite powders were prepared using solid-state reaction via in-situ method. Li6Zr2O7 existed in the ceramic powders at low calcination temperatures. When the calcination temperature was increased to 900 °C, Li6Zr2O7 was transformed into Li2ZrO3 due to the decomposition of Li6Zr2O7 at high temperatures. The TEM observation confirmed that the powders consisted of Li4SiO4 and Li2ZrO3. The Li4SiO4 and Li4SiO4-xLi2ZrO3 (x = 0.5, 1) pebbles were fabricated by the sol-gel method. The measurement results showed that the pebbles had a narrow size distribution and fine sphericity. The density of Li4SiO4-Li2ZrO3 pebbles reached 96.01% of the theoretical density when it was sintered at 1000 °C for 4 h. Compared with the Li4SiO4, the grain size of ceramic pebbles was significantly reduced. Owing to decreased grain size, 139.0 N crush load for the pebbles and 92.4 MPa bending strength for the sintered bodies were achieved. Besides, the ceramics with the Li4SiO4 to Li2ZrO3 ratio of 2: 1 exhibited preferable mechanical properties. Further, to investigate the chemical stability of biphasic ceramics, the structure and mechanical properties were examined under high temperatures and continuous inert gas purging, simulating the working condition of fusion reactors. It was shown that there was almost no change in phase composition and grain size after purging for 60 h at 650 °C. For the mechanical properties, the crush load was decreased initially due to the cracking in the surface region of the ceramic and then increased because the cracking was recovered.