As smart electronics and self-powered devices continue to evolve, the emergence of piezoelectric polymers has sparked significant research interest. In this pioneering project, we have successfully synthesized ZIF-67 particles/tetrabutylammonium hexafluorophosphate (TBAHP)/polyvinylidene fluoride (PVDF) tree-like nanofiber structures for the first time, which was characterized by a large number of branching nanofibers (down to 5 nm) and a uniform diameter trunk fiber (about 400 nm). And the synergistic interaction between these two distinct additives yields exceptional multifunctional properties. By optimizing the quantities of ZIF-67 and TBAHP, we enhanced the β-phase content and piezoelectric performance of PVDF through diameter refinement, interface coupling enhancement, and the introduction of a micro-capacitance mechanism. Notably, the improvements surpassed those achieved with a single additive. Specifically, the piezoelectric energy harvester fabricated using TBAHP/PVDF-TLNMs doped with 0.5 wt% ZIF-67 exhibited an output current of 4.25 μA and a peak voltage of 17.32 V, marking an increase of approximately 1187 % and 831 %, respectively, over pure PVDF nanofiber membranes. Furthermore, the device demonstrated sensitivity to motor movements and effectively harvested energy from diverse bodily motions.