Two polybutadiene rubbers (BR) with different 1,4- cis content were used to prepare compounds with a cure system based on sulfur and TBBS (N-t-butyl-2-benzothiazole sulfenamide). Torque curves, measured with a moving die rheometer at a temperature of 433 K, were used to characterize the vulcanization process. Vulcanization kinetics of the two BR compounds was studied using the formalism proposed by Kamal and Sourour. To vary the cure level, samples of each compound were vulcanized at 433 K at different times, according to the information obtained from the rheometer data. From swelling data, the diffusion coefficient of toluene in BR was evaluated, taking into account the influence of polymer structure and crosslink density.