Greatly enhanced energy density in poly(vinylidene fluoride‐chlorotrifluoroethylene) P(VDF‐CTFE) is realized through interface effects induced by a photo cross‐linking method. Being different from nanocomposites with lowered dielectric strength, the cross‐linked P(VDF‐CTFE)s possess a high breakdown field as well as remarkably elevated polarization, both of which contribute to the enhanced energy density as high as 22.5 J · cm−3. Moreover, patterned thin films with various shapes and sizes are fabricated by photolithography, which sheds new light on the integration of PVDF‐based electroactive polymers into organic microelectronic devices such as flexible pyroelectric/piezoelectric sensor arrays or non‐volatile ferroelectric memory devices. Greatly enhanced energy density in P(VDF‐CTFE) is realized through interface effects induced by a photo cross‐linking method. The cross‐linked P(VDF‐CTFE)s possess high breakdown field as well as remarkably elevated polarization, both of which contribute to the enhanced energy density as high as 22.5 J·cm−3. Patterned thin films with various shapes and sizes are fabricated by photolithography, which sheds new light on the integration of PVDF‐based electroactive polymers into micro organic electronic devices.