The BaCuSi4O10 (Chinese blue) was prepared by coprecipitation and hydrothermal process at 180 degrees C for 20 h prior to sintering at 800 degrees C with a final pigment of superior performance. The crystalline configuration and microstructure of the product were characterized by XRD, FTIR, SEM and TEM. The electronic structure and the valence situation were determined by XPS. The coloration was studied with colorimeter. The absorption and the luminescence properties were examined with an UV-VIS-NIR spectrometer and a spectrofluorimeter, respectively. The results show that the BaCuSi4O10 pigment prepared by this combined fabrication process possesses flower-like mesoporous microspheres morphology, better crystallization, clear coloration and rather qualified purity. The as-prepared BaCuSi4O10 pigment also shows well optical property with broadband absorption and better emission in the 800-1200 nm range. Compared with traditional solid state fabrication or only sole hydrothermal process, this novel process can also reduce hydrothermal temperature and time, and decrease calcination temperature.