Low‐temperature co‐fired ceramic (LTCC) with middle permittivity is very crucial to the miniaturization of components. Based on our previous study on the glass/CaTiO3‐TiO2 composite, prefiring temperature and particle size of CaTiO3‐TiO2 ceramic were optimized in this study to promote the performance of the composites. Comparing with our previous study, after being sintered with 50 wt% glass at 875°C, CaTiO3‐TiO2 ceramic prefired at 1275°C with particle size of 3.38 μm showed excellent properties of sintering density = 3.33 g/cm3, εr = 30.2, tan δ = 0.0005 (7 GHz). In addition, surface roughness of green tapes was also improved after optimization. The material has a good chemical stability and shrinkage matching with silver, making it a very promising candidate material for LTCC applications.