Controllable conversion of biomass to value-added carbon materials is attractive towards a wide variety of potential applications. Herein, hydrothermal treatment and KOH activation are successively employed to treat the cheap and abundant camellia oleifera shell as a new carbon raw material. It is shown that this stepwise activation process allows the production of porous nitrogen-doped carbon with optimized surface chemistry and porous structure compared to the counterparts prepared by a single activation procedure. Benefiting from the modulated porous structure, the as-produced porous nitrogen-doped carbon electrode delivered a high reversible capacity of 1080 mAh g-1 at a current density of 100 mA g-1, which is 3.3 and 5.8 times as high as that of the carbon materials prepared by bare hydrothermal treatment or KOH activation, respectively. Moreover, the optimized surface composition of the porous nitrogen-doped carbon endows it with a highest initial Coulombic efficiency among the three samples, showing great potentials for practical applications. This work is expected to pave a new avenue to upgrade biomass to carbon materials with tunable surface properties and microstructures for target applications.