Nanocomposites of poly(vinyl alcohol) (PVA) with Mg-Al layered double hydroxides (LDHs) were prepared with different compositions, viz., 2, 4, 6, and 8 wt %, of LDH, by solution-intercalation method. The effect of LDH contents on thermal, physicomechanical, and morphological property of PVA films were investigated. Differential scanning calorimetric analysis reveals that LDH layers promote a new crystalline phase for PVA. The tensile analysis of PVA/LDH nanocomposites indicates reduction in tensile strength and modulus with change in LDH concentration and moisture. The microstructure analysis by optical microscopy and scanning electron microscopy demonstrates exfoliation and dispersion of LDHs in the PVA matrix in a disorderly fashion. The primary focus of the present investigation is to explore the potential of LDHs as nanofiller in a polyhydroxy polymer without surface modification. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116:1671-1677,2010