The sulfur cross-linking and the reinforcement by filler are the two most important issues governing the vulcanizate properties of rubber. Lots of various studies have been carried out to gain better understanding of the two. The findings have enlightened rubber industry practitioners and rubber researchers. However, there are still unknown aspects on the vulcanization and the filler-fillings for rubbers. Therefore, it is now necessary to more deeply research essential natures of the sulfur cross-linking and the reinforcement in order to achieve a paradigm shift of rubber science and technology. In this presentation, sulfur cross-linking reagents are shown to play important roles not only to link the rubber chains but also to control the network morphology for the reinforcement of rubber. Zinc is a main key for the two roles. A new reaction mechanisms via bridging bidentate zinc/stearate complexes for N-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine accelerated vulcanization of isoprene rubber is introduced to support the idea. Feature of inhomogeneous network structures in vulcanizates is also presented to characterize a reinforcement effect of network domains in a rubber matrix. The novel insights are important for rubber industry in the future.