Porous carbon materials (PCs) were prepared via hydrothermal carbonization from calcium lignosulfonate (CL) based on enzymatic hydrolysis and alkali activation. The effects of enzymatic hydrolysis and different KOH feeding ratios on the structure and electrochemical properties of enzymatic hydrolysis CL (EHCL)-derived PCs were evaluated in detail. The results showed that the EHCL-derived PCs showed a higher SSA than that of CL. When the mass ratio of KOH/EHCL was 3/2, the PCs exhibited a honeycomb-like microscopic morphology with a specific surface area of up to 1771 m2/g and a 3D hierarchical porous structure composed of abundant micropores, mesopores, and macropores. As an electrode in a supercapacitor, the highest specific capacitance was 147 F/g at a current density of 0.25 A/g, and it maintained 78% of the initial value at a high current density of 10 A/g. The excellent electrochemical cycle and structural stability were confirmed on the condition of a higher capacitance retention of 95.2% after 5000 times of galvanostatic charge/discharge. This work provides a potential application of CL in high-performance supercapacitors.