Solid-state F-19 NMR in combination with fast magic angle spinning at a speed of 35 liHz has been applied to examine the morphology of poly(vinylindene fluoride) samples by effectively suppressing dipolar interactions of the same order. A Lorentzian lineshape fitting analysis applied to the fast magic angle spinning spectrum was able to determine accurately the relative contents for the various domains: crystalline phase, 41%; amorphous regions, 54%; defect segments, 5%; with +/-3% error Limits. Chemical shift anisotropies were also retrieved from sideband intensities: the amorphous component showed rather small anisotropy compared to that of the crystalline domain. Phase separation, in terms of the crystalline and non-crystalline domains, was distinguished by 2D spin exchange experiments, where cross-peaks were found not to be caused by chain conformation reorientations, but instead by spin diffusion. Evidence of the spin diffusion behavior mediated by unsuppressed homonuclear dipolar interactions has allowed us to examine molecular proximity under fast MAS conditions. (C) 2000 Elsevier Science Ltd. All rights reserved.