The CaZrO3 complex oxide ceramic was synthesized in the development of the potential refractory for melting of titanium alloy, the crucible ( 40XH40mm) was prepared by the solid sintering of mixture of powder (CaO:ZrO2 =1:1) with a small amount of TiO2 as additive at 1750°C. The melting of TiNi and Ti6Al4V was carried out in the inducting furnace under vacuum or/and Ar atmosphere. The interfacial reaction between the melts of alloys and CaZrO3 refractory was investigated by scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDS). It is found that, the thickness of interfacial reaction layer between the ceramic CaZrO3 and the melt of titanium alloys (TiNi and Ti6Al4V) is approximately 30-300 μm, there are few elements such as Ca, Zr, Ti, and Ni diffused through the interfacial reaction layer. These results may provide the basement to designing a novel refractory for melting of titanium alloys.