The preparation of porous materials is an interesting field for a huge variety of potential applications. Herein we report an efficient and convenient strategy for the creation of inverse colloidal crystal structures based on soft core/shell polymer particle templating. This single-source strategy is based on starved-feed emulsion polymerization of hybrid core/shell particles consisting of a poly(methyl methacrylate-co-allyl methacrylate) (P(MMA-co-ALMA)) core and a poly(ethyl acrylate-co-(3-methacryloxypropyl-trimethoxysilane)) (PEA-co-PMEMO) shell. The resulting monodisperse particles are analyzed with respect to their size and distribution by transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. The hybrid monodisperse core/shell particles can be aligned to a colloidal crystal by using the convenient melt-shear organization technique. As a result, free-standing and crack-free hybrid polymer colloidal crystal films are accessible without the need of any solvent or dispersion medium. The processing step is investigated regarding different parameters comprising temperature and pressure for the influence on the colloidal crystal film formation. Furthermore, resulting core/shell ratio is tailored by starved-feed emulsion polymerization conditions, since the ratio affects the quality of the porous structure after thermal treatment of colloidal crystal films. The incorporation of alkoxysilane-containing monomers offers a unique crosslinking strategy that yields mechanically robust and thermally stable films. Due to the increased stability, a removal of PMMA cores is possible by thermal treatment of the templating colloidal crystal films leading to almost isoporous free-standing hybrid materials as determined by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM).