We report a scalable fabrication strategy for flexible piezoelectric nanofiber transducers through a single-nozzle, self-assembling electrospinning process. Unlike traditional coaxial methods, this approach exploits the surface energy differential between polyvinylidene fluoride (PVDF) and multi-walled carbon nanotubes (MWCNTs) to drive the spontaneous formation of a core-shell architecture. The resulting 80 nm diameter fibers feature a predominantly crystalline β-phase PVDF shell, with molecula