The design and development of self-charging supercapacitor power cells are rapidly gaining interest due to their ability to convert and store energy in an integrated device. Here, we have demonstrated the fabrication of a self-charging supercapacitor using siloxene sheets as electrodes and siloxene-based polymeric piezofiber separator immobilized with an ionogel electrolyte. The self-charging properties of the fabricated device subjected to various levels of compressive forces showed their ability to self-charge up to a maximum of 207 mV. The mechanism of self-charging process in the fabricated device is discussed via "piezoelectrochemical effect" with the aid of piezoelectrochemical spectroscopy measurements. These studies revealed the direct evidence of the piezoelectrochemical phenomenon involved in the energy conversion and storage process in the fabricated device. This study can provide insight towards understanding the energy conversion process in self-charging supercapacitors, which is of significance considering the state of the art of piezoelectric driven self-charging supercapacitors.