AbstractControlling the microstructure of biomass‐derived carbon is of essential importance for directing its use. Herein, a hollow spherical carbon (HSC) was prepared from corncob lignin through spray drying and subsequent heat treatment. The HSC, which is characterized by its hierarchically porous structure, delivers high rate capability when it is directly used as electrode material for supercapacitors. This strategy that uses lignin as the precursor avoids the intrinsic difficulty in tuning the microstructure of the biomass‐derived carbons and is suitable for mass production for practical use.