High volumetric energy density is demanding for space-limited applications such as electric vehicles (EVs) and portable mobiles. Supercapacitors have better cyclic and power capabilities compared to batteries; they are still restricted by low volumetric capacity due to low density of active materials (< 0.75 g/cc of AC) and intrinsic non-Faradaic charge storage process. To resolve these challenges, we demonstrate ultrahigh volumetric capacitance of conducting polymer networks through the pseudocapacitance with significant durability. The charge storage mechanism of the as-designed conducting polymer hybrid networks for the exceptional volumetric pseudocapacitance was deeply investigated by in-situ ATR-FTIR spectroscopic and ex-situ XPS analyses. The results will inspire to architecture other organic hybrid networks in an analoguous manner for new energy storage materials and put forth new avenue for the design of high volumetric energy storage materials through the redox charge transfer.