PbZr0.4Ti0.6O3 multilayer, comprising of three PbZr0.4Ti0.6O3 stacks with a slight difference in their periodic thickness, has been designed and fabricated on FTO substrate based on one single chemical solution and on the simple spinning-coating and annealing technique. The obtained multilayer exhibits a high reflectivity band with 110 nm photonic stop-band width and average reflectivity of over 80% at room temperature, rendering the novel arrange of PbZr0.4Ti0.6O3 multilayer system a promising candidate as tunable dielectric mirrors, optical cavities and selective filters.