It is reported that Li ions can contribute a lot to the capacitance of aqueous Li-ion capacitors (LICs), which might be due to the intercalation/de-intercalation processes of Li+ ions that also occur at the anodes. However the energy storage mechanism in the aqueous LIC system still requires further proof. In this work, a type of aqueous fiber-shaped LIC has been designed and developed using hydrogenated Li4Ti5O12 (H-LTO) anodes, active carbon (AC) cathodes, and LiCl/PVA gel electrolytes with a double-helical structure. The obtained single LTO wire electrode exhibits a high specific capacitance in volume (34.1 F cm-3) and superior cycling stabilities (∼100% over 100 000 cycles), both of which are due to the formed amorphous layers at the surface of the electrodes. Moreover, it is found via sweep voltammetry analysis that most of the energy stored in an aqueous fiber-shaped capacitor electrode is attributed to the Li ions' intercalation, whose content exceeds 85% at a low scan rate and gradually decreases with increasing scan rate; while the energy stored by the double electric layers remains almost unchanged with different scan rates. Furthermore, the well-matched wearable fiber-shaped LICs show high capacitive behaviors (18.44 μW h cm-2) and superior static/dynamic cycling stabilities. This research would provide some insight into the charge storage mechanism in electrodes in the aqueous system, and give more suggestions to develop high-energy-density fiber-shaped energy storage devices.