Organosilyl-modified and star-shaped poly (${varepsilon}$-caprolactone) (m-PCL) was prepared, and added to polymethylsilsesquioxane (PMSSQ), to make composites. The end groups of m-PCL are chemically similar to PMSSQ, and m-PCL mixed well with PMSSQ in the composite. Porous PMSSQ film was made by further calcination of the composite film at elevated temperature. m-PCL-templated PMSSQ and the as-prepared porous PMSSQ were structurally, optically, and thermally characterized in thin films. The chemical binding of m-PCL and PMSSQ effectively suppressed the phase separation of PMSSQ and m-PCL during the curing process. After calcination at elevated temperature, there remained many pores in the PMSSQ matrix. The refractive indices of the resulting porous PMSSQ thin films decreased with increase of the film porosities, depending on the initial m-PCL loadings.