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An understanding of the structural evolution in micro-/nano-layer co-extrusion process is essential to fabricate high-performance multilayered products. Therefore, in this work, we reveal systematically the multiscale structural development, involving both the layer architecture and microstructure within layers of micro-/nano-layer coextruded polymer films, as well as its relationship to dielectric properties, based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/polycarbonate (PC) system. Interestingly, layer architectur