Abstract: Ordered arrays with a face-centered cubic lattice of PLZT-SiO₂ composites were fabricated by synchronous-assembly approach because it′s simplicity to form opal-like PCs and that avoids the complicated multi-step procedures.Global PLZT particles in the range of 20nm to 40nm were obtained by decomposition of PLZT peroxide precursor.Ultra fine particles can be simultaneously packed around the colloid spheres to form opal of core-shell structure when the solvent is removed through evaporation at 60℃.Mass ratio of silica to PLZT in the mixture is 10:1 while the concentration of silica is 0.25%.Compact shells of PLZT are obtained after being calcined at 650℃ for 12h.