The utilization of wood-derived carbon thick electrodes has demonstrated remarkable structural advantages in the realm of electrochemical energy storage and catalysis. Its exceptional structural stability, mechanical strength, and well-organized pore structure position it as a promising material for self-supporting electrodes. The multi-scale cross-linking of lignin, cellulose, and hemicellulose within the wood tracheid wall establishes a convenient prerequisite for structural modification. However, the significance of dynamic nanopores on wood tracheid walls in enhancing the microporous/mesoporous structure of wood-derived carbon electrodes has been overlooked due to the focus on operability of microscale array pores and wood decomposition processes. Here, we employ a straightforward, highly efficient, and environmentally sustainable solvent infiltration strategy to enhance the nanopore content within the wood tracheid wall, ultimately resulting in a significant enhancement of the microporous/mesoporous composition within the wood-derived electrode. The charge storage capacity of wood-derived carbon electrode is doubled through the implementation of a solvent permeation modification strategy, while its abundant micro/mesoporous structure also endows it with significant potential in the field of electrocatalysis. Therefore, this thermal and solvent permeation modification strategy is anticipated to supplant the conventional acid-base etching method and offer a novel research concept for the advancement of wood-based carbon electrodes with abundant pore structure and exceptional electrochemical properties.