Crosslinking junctions of vulcanized natural rubber were analyzed by solid-state NMR spectroscopy equipped with a field-gradient high speed magic angle spinning probe. Resolution of H-1 and C-13 NMR spectra and correlations between H-1 and C-13 of the vulcanized natural rubber were investigated by one- and two-dimensional measurements, including inverse correlation measurements. The number of substitution of the carbon atom at the crosslinking junctions was determined by solid-state NMR spectroscopy. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.