A 3D network composed of V2O5 nanofibers was manufactured on a novel conductive printing paper urea–LiClO4–PVA (ULP) deep eutectic solvent gel-doped graphite/printing paper, U-paper for use as electrodes linked with a ULP neutral gel electrolyte for 3D network V2O5 wearable symmetric pseudocapacitors (WSSCs). The function of the ULP gel is not only that it can be doped into the conductive ink to decrease the resistance of the conductive printing paper but also that it increases the stability of V2O5-based electrodes. Moreover, 3D network V2O5 WSSCs containing the ULP gel can support high operating voltages of 4.0 V with great specific capacitance (160 F/g) and offer a high energy density (355 W h/kg at 0.2 kW/kg). The 3D network V2O5 WSSCs exhibit a superior cycling stability/durability after 5000 cycles (capacitance retention of ∼91%). Operando X-ray absorption spectroscopy experiments show the reversibility and pseudocapacitive properties of V2O5 from the ULP gel and offer the information of the oxidation states of vanadium during charge–discharge cycles. The 3D network V2O5 WSSCs with the ULP gel electrolyte show great potential prospective candidates for smarter 3D wearable energy-storage devices and Internet-of-Things applications.