The limited specific surface area (SSA), long preparation period, and high cost are significant challenges for carbon xerogels (CXs). To overcome these limitations, we propose an approach to prepare tannin-resorcinol-formaldehyde-based CXs through template-catalyzed in situ polymerization. ZnCl 2 acts as a catalyst and significantly accelerates the polymerization reaction through the coordination of Zn 2+ to the carbonyl group in formaldehyde, while atmospheric drying instead of special drying and without solvent exchange reduces the preparation period to 24 h. In addition, ZnCl 2 acts as an activator for the formation of many pores. Plant-derived tannins not only reduce the preparation cost but also regulate the pore structure. The resulted CXs with hierarchical porous structures show an optimal SSA of 1308 m 2 /g, high adsorption capabilities (for cationic, nitrosoaniline dyes, metal, and nonmetallic ions, especially for methylene blue with 454.93 mg/g), low shrinkage down to 10%, and reusability with 92.9% retention after 5 cycles. This work provides a promising and costeffective method for the large-scale preparation of porous carbon materials with large SSA, offering potential applications in adsorption, energy storage, and catalysis.