Despite the significant potential of organic piezoelectric materials in the electro-mechanical or mechano-electrical applications that require light and flexible material properties, the intrinsically low piezoelectric performance as compared to traditional inorganic materials has limited their full utilization. In this study, we demonstrate that dimensional reduction of poly(vinylidene fluoride trifluoroethylene) (P(VDF-TrFE)) at the nanoscale by electrospinning, combined with an appropriate thermal treatment, induces a transformative enhancement in piezoelectric performance. Specifically, the piezoelectric coefficient (d33) reached up to -108 pm V-1, approaching that of inorganic counterparts. Electrospun mats composed of thermo-treated 30 nm nanofibers with a thickness of 15 μm produced a consistent peak-to-peak voltage of 38.5 V and a power output of 74.1 μW at a strain of 0.26% while sustaining energy production over 10k repeated actuations. The exceptional piezoelectric performance was realized by the enhancement of piezoelectric dipole alignment and the materialization of flexoelectricity, both from the synergistic effects of dimensional reduction and thermal treatment. Our findings suggest that dimensionally controlled and thermally treated electrospun P(VDF-TrFE) nanofibers provide an opportunity to exploit their flexibility and durability for mechanically challenging applications while matching the piezoelectric performance of brittle, inorganic piezoelectric materials.