AbstractVulcanizates obtained from the sulfur vulcanization of natural rubber using a combination of the accelerators N‐cyclohexylbenzothiazole‐2‐sulfenamide (CBS) and tetramethylthiuram disulfide (TMTD) have been analyzed in terms of the numbers of poly‐, di‐, and monosulfide crosslinks, network‐bound accelerator residues, and cyclic sulfide chain modifications as a function of cure time. The vulcanization system produced mainly monosulfide crosslinks at optimum cure, although there were differences in detail between this mixed system and a previously reported efficient sulfur vulcanization (EV) system using a high ratio of CBS to sulfur.