Investigations have been carried out on the effect of several zinc dithiocarbamates in the presence of thiazole-based accelerators in the vulcanization of natural rubber (NR), keeping in mind the possibility of introducing safe dithiocarbamates derived from safe amines. Mutual activity is observed in all the binary systems studied, the highest being observed in the zinc dibenzyldithiocarbamate dibenzothiazyldisulfide (ZBEC-MBTS) -accelerated system. The effect of zinc diisopropyl dithiophosphate, reportedly a safe rubber additive, which is recognized as an age-resistant agent for NR, on cure has also been studied. The study reveals that thiuram disulfide and MBT are always formed from the reaction either between zinc dithiocarbamate (ZDC) and MBTS or between ZDC and N cyclohexyl-2-benzothiazole sulfenamide (CBS). It has been conclusively proved that 2-mercaptobenzothiazole (MBT) generated from MBTS or CBS reacts with ZDC and produces tetramethyl thinram disulfide (TMTD). The observed mutual activity has been discussed based on the cure and physical data and explained through the results based on HPLC and a reaction mechanism.