Silicon-based supercapacitors are highly essential for the utilization of supercapacitor technology in consumer electronics, owing to their on-chip integration with the well-established complementary metal-oxide-semiconductor-related fabrication technology. In this study, silicon nanowalls were carved on commercially available silicon wafers by using a facile, low-cost and complementary metal-oxide-semiconductor compatible method of metal (silver)-assisted chemical etching. The electron microscopic studies of the carved out silicon nanowalls reveal that they are smooth, single crystalline and vertically aligned to their base silicon wafer. Raman and ATR-FTIR spectroscopy confirm that the surface of the silicon nanowalls has Si-O-Si bonded structures. Cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) studies were carried out in the organic electrolyte tetraethylammonium tetrafluroborate (NEt4BF4) in propylene carbonate (PC). It is evident from both the CV and GCD studies that the silicon nanowalls exhibit redox peaks arising from the silver-related deep-level trap state in silicon in contact with adsorbed water and also from the oxidation of silicon and its hydrides by the water present in the electrolyte. The presence of silver in silicon nanowalls and water in the electrolyte are considered to be due to the minute amount of silver left over during its removal by HNO3, owing to the bunching of nanowalls and the highly moisture sensitive nature of the electrolyte, respectively. The influence of such redox peaks on capacitance and cycle life are discussed.