Styrene-butadiene rubber (SBR) is widely used in tires in the automotive segment and vulcanization using sulfur is a common process to enhance its mechanical properties. However, the addition of sulfur as the cross-linking agent usually results in impurities in pyrolysis products during rubber recycling, and thus the desulfurization during tire pyrolysis attracts much attention. In this work, the pyrolysis of vul-canized SBR is studied in detail with the help of ReaxFF molecular dynamics simulation. A series of cross-linked SBR models were built with different sulfur contents and densities. The following ReaxFF MD sim-ulations were performed to show products distributions at different pyrolysis conditions. The simulation results show that sulfur products distribution is mainly controlled by sulfur contents and temperatures. The reaction mechanism is proposed based on the analysis of sulfur products conversion pathway, where most sulfur atoms are bonded with hydrocarbon radicals and the rest transfer to H2S. High sulfur con-tents tend to the formation of elemental sulfur intermediate, and temperature increase facilitates the release of H2S.