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Si69 and Si75, typical commodities of silane coupling agents, are often employed in tire recipes to work as the bridges connecting silica and polymers, with which rolling resistance and wet traction are enhanced without loss in abrasion resistance. In this article, the reactivities of Si69 and Si75 with silica and various rubbers were theoretically investigated by using density functional theory (DFT). When the agents were coupled with silica, not only the acid+water condition but also the pure acid condition was confirmed to readily trigger the condensation reactions. The corresponding Gibbs free energy barriers were related to the charge distributions of reaction regions. As the agents suffered from the homolysis of central SS bonds, the generated single‐S‐tailer radicals (RS·) showed significantly higher reactivities of both the radical addition and the α‐H transfer reactions with rubbers, due to the stronger radical philicities of the terminal sulfur radicals with larger condensed local softnesses [s0(S)]. When the agents underwent the heterolysis of central SS bonds, the terminal sulfur anions with smaller s−(S) indices, however, facilitated the nucleophilic addition reactions with rubbers. Several derivative indices based on the condensed local softnesses were also proposed here to shed light on the reactivities from the viewpoint of the relationship between energy barriers and electronic characteristics. The above findings pave the way for the design of new kinds of silane coupling agents using computer‐aided techniques, and meanwhile, provide references for the practical application of Si69 and Si75 to the silica/rubbers systems. [ABSTRACT FROM AUTHOR]