Porous carbon materials are widely used in particulate forms for energy applications such as fuel cells, batteries, and (super) capacitors. To better hold the particles together, polymeric additives are utilized as binders, which not only increase the weight and volume of the devices, but also cause adverse side effects. We developed a wood-derived, free-standing porous carbon electrode and successfully applied it as a cathode in Li-O₂ batteries. The spontaneously formed hierarchical porous structure exhibits good performance in facilitating the mass transport and hosting the discharge products of Li₂O₂. Heteroatom (N) doping further improves the catalytic activity of the carbon cathode with lower overpotential and higher capacity. Overall, the Li-O₂ battery based on the new carbon cathode affords a stable energy efficiency of 65% and can be operated for 20 cycles at a discharge depth of 70%. The wood-derived free-standing carbon represents a new, unique structure for energy applications.