The curing process of NR with different CBS/S-ratios was studied in order to get more information about the mechanism of the accelerated sulfur vulcanization. Time dependent collected extracts of the vulcanizates were analyzed by means of HPLC-MS and HPLC-UV. The MS-analysis shows the existence of dibenzothiazolyl-polysulfides during the scorch period. Quantitative analysis of the soluble reaction products demonstrates the influence of the sulfur-accelerator-ratio to the disproportion of the accelerator and the rate of the crosslinking reaction.