The diffusion and transport of inhibitor-free styrene through crosslinked natural rubber (NR) have been studied at various temperatures. NR has been vulcanized by conventional, efficient, peroxide and mixed vulcanization techniques. The dependence of diffusion coefficient on the crosslinking system has been studied for all the systems. The influence of temperature on the sorption and the activation energies of sorption have been calculated. The interaction parameter, permeability, sorption coefficient and molecular weight between crosslinks have been evaluated using the diffusion data. The effect of degree of crosslinking on the sorption characteristics of styrene through NR has also been investigated for the different crosslinking systems. The peroxide system showed lowest uptake and the conventional system showed highest uptake.