Sulfur vulcanizates of high cis-butadiene rubber (BR) obtained by using different curing systems such as conventional (CBS) and efficient sulfur (sulfur donor, TMTD) vulcanizing systems were investigated in detail using high-resolution magic angle spinning (HRMAS) solid state NMR spectroscopy in order to identify the type of cross-linking sequence and overall molecular structure. DEFT-135 HRMAS spectra recorded at 60 degrees C provided 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 COSY and TOCSY HRMAS experiments, whereas NOESY HRMAS experiments provided the dipolar through space interactions. Comparison of these results with solution NMR data on a BR model compound vulcanizate led to the elucidation of the entire network structure. The C-13 chemical shifts found experimentally appeared to be in good agreement with chemical shifts calculated for the proposed structure. Using the described vulcanizing systems, it was shown that crosslinking proceeds by means of a substitution, rather than addition in contrast with our studies on cyclic disulfides based vulcanization reactions of BR. By using CBS or TMTD as vulcanizing agents, differentiation in sulfur cross-link length could be established, Moreover, the presence of several cyclic sulfides in the vulcanizates was observed and a mechanism for their formation is suggested.