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A special sequence of multilayer, consisting of PbZr0.5Ti0.5O3 and SrTiO3 films, was fabricated using a simple chemical solution deposition. X-ray diffractometer (XRD) measurement reveals that each film in this multilayer has been crystallized into the single perovskite phase. The high-angle annular dark-field scanning transmission electron microscopy (STEM) image shows that the obtained SrTiO3/PbZr0.5Ti0.5O3 multilayer contains three components with different optical thicknesses: dense and porous PbZr0.5Ti0.5O3 layers, together with dense SrTiO3 layers. This multilayer system exhibits superior optical performance, with a peak reflectivity of∼95% and a bandwidth of ∼113 nm, rendering its promising candidate as dielectric mirrors, optical cavities, and selective filters.