Suitable solid adsorbents are demanded for carbon capture and storage (CCS) processes. In this work, a novel microporous polymer is developed by hypercrosslinking of organosolv lignin, which is a renewable resource. Reaction with formaldehyde dimethyl acetal (FDA) via Friedel-Crafts reaction gives microporous networks, with moderate capacity of carbon dioxide but excellent selectivity towards CO2 /N2 mixture as predicted on the basis of ideal adsorption-solution theory (IAST). Pyrolysis of pure organosolv lignin results in microporous carbon powders, while pyrolysis of hypercrosslinked organosolv lignin yields shape-persistent materials with increased CO2 capacity while maintaining very good selectivity.