Poly(methyl-co-cyclosiloxane bearing silsesquioxane)s (P(M-co-CSSQs)) were prepared. Using poly(e-caprolactone) (PCL) as a template, PCL / P(M-co-CSSQ) nanohybrid films were fabricated. The electrical, morphological, and mechanical properties of the PCL / P(M-co-CSSQ) films were investigated. The dielectric constant of a cured PCL / P(M-co-CSSQ) film at 420°C scaled down from 2.55 to 2.05 and refractive index from 1.41 to 1.33 when 20 vol. % of the PCL was admixed with the polymer matrix. The elastic modulus and hardness of the cured PCL / P(Mco- CSSQ) (2:8, vol./vol.) film were 2.50 and 0.32 GPa, respectively, showing dependency on the PCL content.