We report an all-polymer flexible piezoelectric fiber that uses both judiciously chosen geometry and advanced materials in order to enhance fiber piezoelectric response. The microstructured/nanostructured fiber features a soft hollow polycarbonate core surrounded by a spiral multilayer cladding consisting of alternating layers of piezoelectric nanocomposites (polyvinylidene enhanced with BaTiO3, PZT, or CNT) and conductive polymer (carbon-filled polyethylene). The conductive polymer layers serve as two electrodes, and they also form two spatially offset electric connectors on the fiber surface designed for the ease of connectorization. Kilometer-long piezoelectric fibers of sub-millimeter diameters are thermally drawn from a macroscopic preform. The fibers exhibit high output voltage of up to 6 V under moderate bending, and they show excellent mechanical and electrical durability in a cyclic bend−release test. The micron/nanosize multilayer structure enhances in-fiber poling efficiency due to the small distance between the conducting electrodes sandwiching the piezoelectric composite layers. Additionally, the spiral structure greatly increases the active area of the piezoelectric composite, thus promoting higher voltage generation and resulting in 10−100 higher power generation efficiency over the existing piezoelectric cables. Finally, we weave the fabricated piezoelectric fibers into technical textiles and demonstrate their potential applications in power generation when used as a sound detector, smart car seat upholstery, or wearable materials.