A layer-by-layer assembly method was employed to fabricate multilayered films containing the terbium heteropolyanions K-6[Tb(BW11O39)(H2O)(3)](.)32H(2)O and Ky[Tb(XW11O39)(2)](.)nH(2)O (X = Si and P) and the polyelectrolytes poly(4-styrenesulfonate) and poly(allylamine hydrochloride). A comparative study on the optical properties of the films containing distinct polyoxometalates and different types of multilayers was carried out. The photoluminescence of the solid polyoxometalates and of the resulting films was investigated.