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 architecture and morphology show strong dependences on the nominal layer thicknesses. Particularly, with layer thickness reduced to nanometer scale, interfacial instabilities triggered by viscoelastic differences between components emerge with the creation of micro-droplets and micro-sheets. Films show an enhanced crystallization with the formation of two-dimensional (2D) spherulites in microlayer coextruded systems and the oriented in-plane lamellae in nanolayer coextruded counterparts, where layer breakup in the thinner layers further changes the crystallization behaviors. These macro- and microscopic structures, developed from the co-extrusion process, substantially influence the dielectric properties of coextruded films. Mechanism responsible for dielectric performance is further proposed by considering these effects of multiscale structure on the dipole switching and charge hopping in the multilayered structures. This work clearly demonstrates how the multiscale structural evolution during the micro-/nano-layer coextrusion process can control the dielectric properties of multilayered products.