Continuous low-level current (CLLC) measurements for detecting ionic species in the course of vulcanization reactions were applied to investigate the vulcanization of a mixture of natural rubber (NR),sulfur (S), and zinc bis(dimetlhyldithiocarbamate) (ZnDMTC). A de voltage was applied to the reaction mixture in a special vulcanization mold and the current (e.g., in the range of 10(-9) A) was measured. Temperature-dependent current maxima were found after reaction times t(max). The simplest explanation is that transitory ionic species occur during vulcanization. An activation energy (E-alpha) = 116.4 kJ/mol, similar to that obtained in previous chemical investigations, was determined from the decrease of t(max) with increasing temperature. The maxima corresponded to reaction times where a strong increase of polymer crosslinking was observed, as measured using vulcametry. For comparison, de measurements were carried out with the corresponding mixture without elemental sulfur (NR/ZnDMTC) and mixtures containing zinc stearate (ZnST) instead of zinc bis(dimethyldithiocarbamate) (NR/S/ZnST and NR/ZnST).