An advanced energy autonomous system that simultaneously harnesses and stores energy on the same platform offers exciting opportunities for the near-future self-powered miniature electronics. However, achieving optimal synchronization between the power output of an energy harvester and the storage unit or integrating it seamlessly with real-time microelectronics to build a highly efficient energy autonomous system remains challenging. Herein, a unique bimetallic layered double hydroxide (LDH) based tribo-positive layer is introduced for a high-voltage sliding triboelectric nanogenerator (S-TENG) with an output voltage of ≈1485 V and power output of 250 µW, respectively. To demonstrate the potential of a self-charging power system, S-TENG is integrated with on-chip micro-supercapacitors (MSCs) as a storage unit. The MSC array effectively self-charged up to 4.8 V (within 220s), providing ample power to support micro-sensory systems. In addition, by utilizing the high-voltage output of the S-TENG, the efficient operation of electrostatic actuators and digital microfluidic (DMF) systems driven directly by simple mechanical motion is further demonstrated. Overall, this work can provide a solid foundation for the advancement of next-generation energy-autonomous systems.