To improve display performance, refractive index matching between a laminating material and the substrate was considered a crucial interfacial issue in optical stack design. To control the refractive index of the silicone optical laminating material, phenyl groups were introduced into the polymer component. and novel vinyl‐ and phenyl‐terminated MTQ (MviTphQ or MTPQ) resins were prepared by hydrolysis and condensation‐polymerization of a mixture of ethyl polysilicate, phenyltriethoxysilane, and divinyltetramethyl disiloxane to enhance the performance of optical laminating materials. These synthesized resins were utilized to formulate novel high‐refractive‐index silicone optical laminate compositions. The influence of refractive index on light transmittance was measured and compared with theoretical values. The influence of s‐MTPQ resin content on humidity resistance and transparency retention during aging were evaluated as crucial characteristics of an optical laminating material for automotive display applications.