Abstract The mechanism of devulcanization of sulfur-vulcanized natural rubber with aromatic disulfides and aliphatic amines has been studied using 2,3-dimethyl-2-butene (C6H12) as a low-molecular weight model compound. First C6H12 was vulcanized with a mixture of sulfur, zinc stearate and N-cyclohexyl-2-benzothiazylsulfenamide (CBS) as accelerator at 140 °C, resulting in a mixture of addition products (C6H11−Sx−C6H11). The compounds were isolated and identified by High Performance Liquid Chromatography (HPLC) with respect to their various sulfur ranks. In a second stage, the vulcanized products were devulcanized using the agents mentioned above at 200 °C. The kinetics and chemistry of the breakdown of the sulfur-bridges were monitored. Both devulcanization agents decompose sulfidic vulcanization products with sulfur ranks equal or higher than 3 quite effectively and with comparable speed. Diphenyldisulfide as devulcanization agent gives rise to a high amount of mono- and disulfidic compounds formed during the devulcanization, hexadecylamine, as devulcanization agent, prevents these lower sulfur ranks from being formed.