PbZr0.4Ti0.6O3 (PZT) multilayers were prepared by sol-gel method using chemical solutions containing polymer of Polyvinylpyrrolidone (PVP). Effects of PVP content on optical properties of PZT multilayers have been investigated. Tests demonstrated that these multilayers display a layered structure consisting of dense and porous PZT layers and these dense and porous layers are alternately arranged in the layered structure. The reflectance spectra in visible region exhibit a single optical reflection-band with high reflectivity. The central wavelength of the reflection-band shifts to longer wavelength with the increase of PVP concentration within a given polymer content range. The multilayer derived from chemical solution containing PVP with a relative molar ratio of x = 1.0 exhibits the optimal performance with highest optical reflectivity of 89% and largest stop-band width of 44 nm.