In this work, 2-phenylethyl-functionalized (SSR) and 2-methyl-3-methoxy-3-oxopropyl-functionalized silicone rubbers (MSR) were obtained via the platinum(0)-catalyzed hydrosilylation reaction between styrene/methyl methacrylate and polymethylhydrosiloxane. SSR exhibits both sufficient elongation at break (ɛ = 45 ± 5%), tensile strength (σ = 1.5 ± 0.4 MPa) and Young’s modulus, (E = 3.4 ± 0.7 MPa), which is higher than for Sylgard 184 (E = 1.1 ± 0.3 MPa). SSR and MSR are optically transparent and exhibit a low adhesion to a Si substrate. However, MSR possesses lower tensile strength (σ = 0.6 ± 0.1MPa, E = 0.6 ± 0.1 MPa) comparing to SSR. Thus, SSR was applied as a supporting polymer matrix for encapsulation of inorganic NWs arrays for flexible optoelectronics.