Sulfur vulcanization was carried out with cyclooctene, cis-3-heptene, trans-4-octene, cis-1,7-diphenyl-3-heptene, and cis-1-phenyl-3-heptene serving as models of BR and SBR. The dialkenyl sulfanes R2Sn (n = 1-6) obtained as vulcanisation products were separated according to their chain lengths by reversed phase liquid chromatography; the structure of the alkenyl groups was identified by H-1 and C-13 MMR, all vulcanization products result from the substitution of an allylic proton by a sulfur bridge. From the NMR spectra H-1 and C-13 shift increments of SnR groups (R = octenyl) have been evaluated. Whereas C-13 shift increments did not contribute to a better understanding of the C-13 spectra of BW vulcanizates, H-1 shift increments assisted by H,H-COSY experiments led to a partial analysis of the proton spectrum of a Polyoil 110 (low molecular weight polybutadiene) vulcanizate. The assignments of the signals in the proton spectrum to specific structures in the sulfur network could be transferred to the C-13 spectrum by H,C-correlation. At present, mono-, di-, and polysulfidic structures as well as structures containing the mercapto benzothiacyl group of the accelerator can be identified.