As a piezo-polymer, the most contribution of polar phases (β-, γ-phases) to the piezoelectricity of polyvinylidene fluoride (PVDF) has been researched. Herein, a new type PVDF/tetrabutylammonium hexafluorophosphate (TBAHP) tree-like nanofiber membrane (TLNM) with high polar phase content and numerous fine branch fibers was successfully developed via electrospinning. PVDF-TLNMs exhibited mass branch fibers whose diameters of less than 50 nm. The β-phase content of 88.94 % disclosed piezoelectric polarization ability in the presence of TBAHP and tree-like structure. The best output current and voltage of flexible PVDF-TLNMs based piezoelectric nanogenerators (PENGs) could reach 2.04 μA and 4.08 V at 0.07 mol L−1 TBAHP, which increased the current of pure PVDF by approximately six times and a 217 % improvement to voltage output. Likewise, the peak power density of 0.07 mol L−1 PVDF-TLNM was 13 times above that of pure PVDF-NM. The significant reduction of internal resistance occurred after the addition of TBAHP. Such significant enhancements for electrical output depended on the high β-phase content, originated through TBAHP induced self-alignment of electric dipoles in PVDF polymer and high extent of mechanical drawing. The new kind of PVDF-TLNMs-base PENGs can provide a large scope for the ideas of smart wearable devices.