The low surface energy of silicone rubber (SiR) makes it difficult to blend SiR with conventional rubbers such as solution styrene−butadiene rubber (SSBR) and natural rubber. In this study, to enhance the interface interaction between SiR and SSBR, trimethylolpropane tris(3-mercaptopropionate) (TMPMP) was carefully chosen to couple SiR and SSBR by in-situ thiol-ene click reactions between mercapto groups of TMPMP and vinyl groups of SiR and SSBR. The reaction of TMPMP with SiR and SSBR was characterized via torque−time curves, element analysis, and the dissolving−swelling test. To overcome the low reactivity of TMPMP with SiR containing low-vinyl-content, a two-step strategy was proposed to prepare low-vinyl-content SiR/SSBR composites, where TMPMP reacted with SiR first. Transmission electron microscopy indicated that the two-step strategy reduced the phase domain size of the blend. Furthermore, the tailor-synthesized high-vinyl-content SiR/SSBR composite achieved better interface interaction via a one-step in-situ interface coupling strategy. The corresponding composite exhibited higher mechanical properties and lower hysteresis at 60 oC. The results would extend the applications of SiR.