Two-dimensional infrared (2D IR) correlation spectroscopy was applied to study the conformation change during poly(vinylidene fluoride) (PVDF) melting process. The absorption spectral changes are observed with increasing temperature. These observed changes in IR spectra might be attributed to three kinds of PVDF components: alpha-PVDF, beta-PVDF, and amorphous component. 2D IR correlation analysis indicates that during melting process three kinds of PVDF component change asynchronously: above all, the amorphous component relaxes its molecule chains, and then the P-PVDF transfers to amorphous component, finally the alpha-PVDF transfers to amorphous component. (C) 2004 Elsevier Ltd. All rights reserved.