PbZr0.53Ti0.47O3 (PZT) nanoparticles of size distribution similar to 1-6 nm were synthesized by single-step autoignition of metal-polyvinyl alcohol (PVA) gel. The physical and chemical bonding between the metals ions and PVA in gel was analyzed from the results of the characterization by FTIR, SEM, and XRD techniques. The appearance of a doublet band between 3500 and 3200 cm(-1) and the shifting of stretching frequency of O-H band in the FTIR spectra of gel indicated strong electrostatic interaction between the metal ions and the polar OH groups of the polymer. The electrostatic interaction decreased the extent of hydrogen bonding drastically due to engagement of Polar OH groups in complex formation with the metal ions. Microstructural study of the dried gel by SEM coupled with its FTIR analyses indicated crosslinking in the metal-polymer gel. The loss of crystallinity of PVA in gel detected by XRD also indicated the drastic degradation of hydrogen bonding in PVA due to the formation of coordination complex with the metal ions. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 110: 26932697, 2008