The low energy density and low cost performance of electrochemical capacitors (ECs) are the principal factors that limit the wide applications of ECs. In this work, we used enzymatic hydrolysis lignin as the carbon source and an ammonia activation methodology to prepare nitrogen-doped lignin-derived porous carbon (NLPC) electrode materials with high specific surface areas. We elucidated the free radical mechanism of ammonia activation and the relationship between nitrogen doping configurations, doping levels, and preparation temperatures. Furthermore, we assembled NLPC∥NLPC symmetric ECs and NLPC∥Zn asymmetric ECs using aqueous sulfate electrolytes. Compared with the ECs using KOH aqueous electrolyte, the energy densities of NLPC∥NLPC and NLPC∥Zn ECs were significantly improved. The divergence of charge storage characteristics in KOH, Na 2 SO 4 , and ZnSO 4 electrolytes were compared by analyzing their area surface capacitance. This work provides a strategy for the sustainable preparation of lignin-derived porous carbons toward ECs with high energy densities.