Silica is the rubber industry’s most essential and cost-effective reinforcing filler after carbon black. The silica reinforcement mechanism with a non-polar elastomer is complicated by the presence of polar functional groups on the silica surface. This polar nature of silica causes filler-to-filler interaction by forming hydrogen bonds. Therefore, sizeable non-dispersed silica clusters remain in a non-polar rubber matrix. To avoid these strong filler-filler interactions and improve rubber/silica compatibility, the silica surface needs to be modified. This can be done using a coupling agent which has functional groups capable of linking both the rubber and silica. It has been discovered that when silica/silane coupling agents are present, the critical properties like rolling resistance and wet grip in the magic triangle of tire tread balance out better than carbon black formulations, bringing the system closer to the green tire goal. In this review article, the efforts made by both the rubber formulation development and chemistry to fully exploit the potential of silica/silane reinforcement for automotive tires are retrospected. Highlights on how compounding ingredients, process technology, functionalized elastomer, novel silanes, and the variant of silicas can enhance the magic triangle and silica-silane reaction mechanism are provided. In addition, the kinetics of silanization and measurements for the degree of silanization is also highlighted. Future research directions in this area are also touched upon. Hopefully, this review can stimulate future silica/silane scientific and technology developments for both academic and industrial-oriented requirements.