The 3D micro- and nanostructure of wood has extensively been employed as a template for cost-effective and renewable electronic technologies. However, other electroactive components, in particular native lignin, have been overlooked due to the absence of an approach that allows access of the lignin through the cell wall. In this study, we introduce an approach that focuses on establishing conjugated-polymer-based electrical connections at various length scales within the wood structure, aiming to leverage the charge storage capacity of native lignin in wood-based energy storage electrodes. We demonstrate that poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) PEDOT/PSS, integrated within the cell wall lumen, can be interfaced with native lignin through the wood cell wall through in situ polymerization of a water-soluble S-EDOT monomer. This approach increases the capacitance of the conductive wood to 315 mF cm-2 at a scan rate of 5 mV s-1, which is seven and, respectively, two times higher compared to the capacitance of conductive wood made with the single components PEDOT/PSS or S-PEDOT. Moreover, we show that the capacitance is contributed by both the electroactive polymers and native lignin, with native lignin accounting for over 70% of the total charge storage capacity. We show that accessing native lignin through in situ creation of electrical interconnections within the wood structure offers a pathway toward sustainable, wood-based electrodes with improved charge-storage capacity for applications in electronics and energy storage.