Biochar is widely used to remove hexavalent chromium [Cr(VI)] from wastewater through adsorption, which is recognized as a facile, cost-efficient, and high-selectivity approach. In this study, a versatile strategy that combines delignification with subsequent carbonization and KOH activation is proposed to prepare a novel woody biochar from waste poplar sawdust. By virtue of the unique multilayered and honeycomb porous structure induced by delignification and activation processes, the resultant activated carbonized delignified wood (ACDW) exhibits a high specific surface area of 970.52 m² g^–1 with increasing meso- and micropores and abundant oxygen-containing functional groups. As a benign adsorbent for the uptake of Cr(VI) in wastewater, ACDW delivers a remarkable adsorption capacity of 294.86 mg g^–1 in maximum, which is significantly superior to that of unmodified counterparts and other reported biochars. Besides, the adsorption behaviors fit better with the Langmuir isotherm, the pseudo-second-order kinetic model, and the adsorption diffusion model in batch experiments. Based on the results, we put forward the conceivable adsorption mechanism that the synergistic contributions of the capillary force, electrostatic attraction, chemical complexation, and reduction action facilitate the Cr(VI) capture by ACDW.