AbstractPoly(vinyl alcohol) (PVA) nanocomposites with pristine sepiolite and heat‐treated (HT) sepiolites were prepared by the method of solution dispersion. The measurements of XRD, FTIR, TEM, and AFM were used for the characterization of the nanocomposites. Furthermore, thermal and optical properties were investigated by TG/DTG/DTA and UV‐visible transmission spectra, respectively. Both the effects of sepiolite/polymer ratio and the structural changes in sepiolite on heating were examined in terms of changes in the properties of the nanocomposites. The addition of sepiolite/HT sepiolites into the PVA matrix resulted in a decrease in the thermal decomposition temperatures of the nanocomposites because of the fact that sepiolite and HT sepiolites facilitated the elimination of the water and acetate groups from the PVA in the second step based on the TG/DTG studies. The HT sepiolites‐PVA nanocomposites had lower thermal stability and more influenced optical clarity than those of the sepiolite PVA, at the same filler levels. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009