In this work, the preparation of highly thermoresponsive and fully reversible stretch‐tunable elastomeric opal films featuring switchable structural colors is reported. Novel particle architectures based on poly(diethylene glycol methylether methacrylate‐co‐ethyl acrylate) (PDEGMEMA‐co‐PEA) as shell polymer are synthesized via seeded and stepwise emulsion polymerization protocols. The use of DEGMEMA as comonomer and herein established synthetic strategies leads to monodisperse soft shell particles, which can be directly processed to opal films by using the feasible melt‐shear organization technique. Subsequent UV crosslinking strategies open access to mechanically stable and homogeneous elastomeric opal films. The structural colors of the opal films feature mechano‐ and thermoresponsiveness, which is found to be fully reversible. Optical characterization shows that the combination of both stimuli provokes a photonic bandgap shift of more than 50 nm from 560 nm in the stretched state to 611 nm in the fully swollen state. In addition, versatile colorful patterns onto the colloidal crystal structure are produced by spatial UV‐induced crosslinking by using a photomask. This facile approach enables the generation of spatially cross‐linked switchable opal films with fascinating optical properties. Herein described strategies for the preparation of PDEGMEMA‐containing colloidal architectures, application of the melt‐shear ordering technique, and patterned crosslinking of the final opal films open access to novel stimuli‐responsive colloidal crystal films, which are expected to be promising materials in the field of security and sensing applications.
