AbstractSulfur vulcanization of natural rubber (NR) and styrene‐butadiene rubber (SBR) accelerated with 2‐mercaptobenzothiazole and zinc oxide with or without stearic acid has been studied and the results compared with those obtained by replacing the thiazole with its zinc salt. The order of the rate of vulcanization as measured from free sulfur decrease or crosslink formation is observed to be unity with respect to time and less than one with respect to accelerator concentration. In absence of stearic acid, the zinc salt is much less efficient than the thiazole in promoting vulcanization, and the efficiency of the latter shows a noticeable improvement over what is attained in absence of zinc oxide. Addition of stearic acid not only raises the efficiency of both the systems to the same level but also leads to a faster rate of vulcanization, a much higher degree of crosslinking, avoidance of reversion, and production of vulcanizates with considerably improved mechanical properties. The formation of zinc sulfide also reveals interesting variation. Attempts have been made to interprete these results in terms of complex formation between zinc salt of thiazole and zinc stear