Vulcanizates of high cis-butadiene rubber (BR) obtained by using several cyclic disulfides such as 1,2-dithiacyclooctane, 1-oxa-4,5-dithiacycloheptane, and 2,3,12,13-tetrathia-[4,4]-metacyclophane, were studied by means of high-resolution magic angle spinning (HRMAS) solid state NMR spectroscopy in order to determine cross-linking sequence and overall molecular structure. DEFT-135 HRMAS spectra recorded at 60 degrees C provided the multiplicity of the different C-13 resonances; interpretation of the HETCOR HRMAS spectra yielded the corresponding H-1 frequencies. Direct and long-range through bond homonuclear connectivities were obtained from HRMAS COSY and TOCSY (rotal correlation spectroscopy) experiments. Comparison of these results with solution NMR data on hexyl disulfide grafted BR and previously described work on a cis,cis,cis-1,5,9-cyclododecatriene (ccc-1,5,9-CDT) based model system led to the elucidation of the entire network structures. The C-13 chemical shifts found experimentally appeared to be in good agreement with chemical shifts calculated for the proposed structures. It was shown that cross-linking proceeds by means of addition of the cyclic disulfides to the carbon double bonds of BR instead of alpha substitution.