Polyisoprene/tetramethylthiuram disulfide (TMTD)/sulfur compounds were vulcanized under a variety of conditions. TMTD does not decompose to tetramethylthiourea (TMTU) at vulcanization temperatures as has been suggested, neither is it formed as an integral part of the crosslinking process. Instead, it results from the attack of dimethylamine, released on decomposition of dimethyldithiocarbamic acid (Hdmtc), on TMTD. It is demonstrated that the formation of TMTU in vulcanizates may be overlooked, as it is readily lost in the work-up for HPLC analysis. Hdmtc is shown to play an essential role in the crosslinking process in polyisoprene/TMTD/sulfur formulations, and its removal from the system during vulcanization severely impedes crosslinking. Polysulfidic thiuram-terminated pendent groups are formed, in part, by the interaction of tetramethylthiuram polysulfides with the polymer chain, but largely by an exchange between Hdmtc and polysulfidic thiol pendent groups. The latter are formed when sulfurated Hdmtc reacts with the polymer chain. Crosslinking of thiuramterminated pendent groups is slow, and in the absence of ZnO crosslinking results from reaction between polysulfidic thiuram pendent groups and thiols. Crosslinking is delayed until the bulk of the accelerator is bound to the polymer chain, at which point the concentration of free thiuram groups, in the form of Hdmtc, is low, and exchanges between newly formed thiol pendent groups and Hdmtc is less frequent, permitting crosslinking of thiuram pendent groups with these newly formed thiol pendent groups. Data to support the proposed reaction mechanism is presented. Hdmtc on its own accelerates sulfur vulcanization and acts as a catalyst for the reaction, being regenerated in the crosslinking process.