Modern demands for efficient, environmentally friendly, and self-powered devices have led to growing interest in piezoelectric polymers in the scientific community. In this paper, a ZIF-67 functionalized polyvinylidene fluoride/ tetrabutylammonium hexafluorophosphate tree-like nanofiber membrane (ZIF-67@PVDF/TBAHP-TLNMs) was developed as piezoelectric nanogenerator for energy harvesting. The ZIF-67@PVDF/TBAHP-TLNMs was prepared by in-situ growth of ZIF-67 on the surface of PVDF TLNMs, which demonstrated remarkable energy harvesting capabilities. The results indicated that the β-phase content of the in-situ growth of ZIF-67 reached 86.94 %, augmented the fiber's rotation radius, and elevated the electromechanical conversion efficiency. Notably, the short circuit current reached 3.87 μA and the output voltage exceeded 9.78 V, which was 10.7 times and 5.9 times higher than the electrical signal output of pure PVDF nanofiber membrane, respectively. Furthermore, the ZIF-67@PVDF/TBAHP-TLNMs exhibited exceptional mechanical properties, with an elastic modulus as high as 1.13 GPa, outperforming other nanofiber membranes and catering to the diverse requirements of wearable devices. During a 500 s test cycle, its layered structure remained intact, without any discernible damage or interlayer separation of the nanofibers. At the same time, the device exhibited high electromechanical conversion efficiency and a sensitive sensing function, which made it have broad application prospects in human motion monitoring and intelligent wearable devices.