The efficient mass transport and enhanced accessibility of active sites are crucial for high-performance electrocatalysts in water splitting. Inspired by the hierarchical structure of natural wood, we engineered a monolithic electrocatalyst, cobalt nanoparticles encapsulated in nitrogen-doped carbon layers on carbonized wood (Co@NC/CW), by carbonizing wood to create a three-dimensional framework with vertically aligned macropores. The unique architecture encapsulates cobalt nanoparticles within in situ-grown nitrogen-doped graphene layers on wood-derived microchannels, facilitating ultrafast electrolyte infusion and anisotropic electron transport. As a result, the optimized freestanding Co@NC/CW electrode exhibits remarkable bifunctional activity, achieving overpotentials of 403 mV and 227 mV for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively, at a current density of 50 mA cm−2. Furthermore, the integrated hybrid electrolyzer combining the HER and the OER delivers an impressive 50 A cm−2 at a cell voltage of 1.72 V while maintaining a Faradaic efficiency near 99.5% and sustaining long-term stability over 120 h of continuous operation. Co@NC/CW also demonstrates performance in the complete decomposition of alkaline seawater, underscoring its potential for scalable applications. This wood-derived catalyst design not only leverages the natural hierarchical porosity of wood but also offers a sustainable platform for advanced electrochemical systems.