A novel flexible solid-sate self-charging supercapacitor was fabricated to address the persisting problem associated with wearable electronics in the case of no electricity or charging source. The all-solid-stat device is designed using a new strategy wherein piezoelectric electrodes are synthesized instead of piezoelectric eletrolyte. The fabricated SCAPSC consists of asymmetric NiSnO3 piezoanode and FeSnO3 piezocathode and PVA-KOH as gel electrolyte. In addition to the high flexibility and considerable electrochemical and self-charging characteristics, the device can also synchronously transformed applied mechanical energy into electrochemical energy via piezoelectrochemical effect. The as-fabricated device can be easily self-charged to 200 mV by simple thumb impact, 155 mV by bending it to 150º, 160 mV by twisting it, and a high value of 266 mV by applying a compressive force of 2 N. The electrochemical analysis of the SCAPSC and the piezoelectrodes revealed that all of them exhibit high specific capacity and high performance. The specific capacitance of the NiSnO3 anode has been recorded to be 742 F g-1, the FeSnO3 cathode to be 2853 F g-1, and the SCAPSC to be 144 F g-1. Apart from flexibity, good self-charging behavior, and high specific capacitance, the fabricated device also attained high-performance which was measured in terms of its energy and power density. The energy density reached45 W h kg–1 at a high power density of 1.25 kW kg–1and sustained 16.25 W h kg–1 at a power density of 22.25 kW kg–1. The siloxene SCSPC can directly convert mechanical energy into electrical energy and store it in a single integrated device with better self-charging properties (superior to many of the reported SCSPC) and good electromechanical stability. Both the NiSnO3 (anode) and FeSnO3 (cathode) achieved a high cyclic stability of 100% at 0.5 A, and 0.95 A, respectively, while the SCAPSC itself had a good cyclic stability of 90% at 0.016 A, after 10,000 repeated GCD cycles. The robustness and wearability of the as-fabricated supercapacitor was tested over a period of days in air and after washing it each time before recording results. The device exhibited good stability both in air as well as after washing it with water. This work can clearly overcome the bottleneck problem toward the charging of electrochemical power sources, and thus paves a new way for the construction of self-powered wearable electronics.