Ferroelectric PbZrB0.4BTiB0.6B0.6OB3(PZT) and BaTi0.9Sr0.1BO3(BST) multilayers were fabricated by a repeated spin-coating/annealing step of using precursors containing polymer additive.Both the multilayers have more than 90% optical reflectivity at a given wavelength range and the maximum reflectivity increases with the number of growth.The microprobe analysis shows that the multilayers exhibit a lamellar structure consisting of alternating dense and porous layers.The possible formation mechanism for the periodical ferroelectric multilayers is examined,which involves phase separation and pyrolysis of polymer.