The advanced flexible wearable self-charging power system (SCPS) offers exciting development prospects for flexible electronics, medical sensing, and environmental monitoring. However, constructing a SCPS with fast charging rate still remains a significant challenge. Therefore, in this study, a flexible SCPS featuring rapid charging rate has been designed. Micro-supercapacitors (MSCs) with a synaptic structure were fabricated via electrospinning technique followed with laser engraving, employing polyethylene glycol diacrylate/sulfuric acid gel and ZIF-8@MXene/carbon nanofibers as the polymer gel electrolyte and electrodes, respectively. The specific capacitance of the synaptic-structured MSCs was measured to be 25.5 F g −1. The power management circuit (PMC) converts the AC output generated by the Ecoflex/BTO triboelectric nanogenerator (TENG) into a stable DC output through periodic conduction, thus greatly reducing the impedance gap between TENG and MSCs, enabling SCPS to efficiently collect high-entropy energy from the environment. The average charging rate could of SCPS reach as high as 26 mV s −1, which is 14.5 times higher than that achieved with a rectifier, and significantly higher than that reported in the literature. The as-prepared SCPS could provide important support for green energy and sustainable development.