The investment casting technology is one of the major methods to produce the parts of the titanium due to its low production cost. However, the high activity of titanium melt gives rise to the requirement of high chemical stability of shell materials, to avoid or decrease the interfacial reaction between the mould and the melt. In this paper, a novel BaZrO₃ – coated Al₂O₃ shell was first introduced to the investment casting of titanium alloy. The grain size and baking temperature on the properties of the novel mould were investigated, and then the Ti6Al4V and TiNi alloys were successfully casted by means of this shell. The alloy-mould interaction was discussed. The results showed that the mould achieve high mechanical properties when the content of coarse powder was 50% after sintering 4 hours under 1500°C, and the BaZrO₃ coating exhibited an effective barrier to avoid the direct contact between the mould base material and the melt, the thickness of reaction layer of TiNi alloy was about 8 μm, and 17 μm to Ti6Al4V alloy, no refractory particles and elemental diffusion were observed inside the metal. This may imply that BaZrO₃ is a promising candidate material for the investment casting of titanium alloy.