Abstract Studies have been made on the mechanism of MBT accelerated sulfur vulcanization of natural rubber containing semi-reinforcing carbon black as a filler. DCP has been used as an aid to distinguish between free radical and polar mechanism. Results indicate that sulfuration by MBT and sulfur proceed by a free radical mechanism but it becomes polar when ZnO and stearic acid are also present. Carbon black does not interfere in the sulfuration but it gives rise to additional crosslinks.