A novel cascade pyrolysis upgrading process for acid hydrolysis lignin (AHL), consisting of pyrolysis, catalytic upgrading of pyrolysis vapors, and pyrolysis char, was developed to improve the yield of value-added products (monophenolic chemicals and carbon materials). Pyrolysis of AHL at 450 °C and subsequent catalytic upgrading of pyrolysis vapors over Ni/H-ZSM-5 boosted the concentration of monophenolic chemicals in pyrolysis liquids by 58%. The carbon material prepared from pyrolysis char using KOH as activating agent exhibited a large specific surface area of 2902.5 m2/g and a large total pore volume of 1.45 cm3/g, thus affording good adsorption capacity for methylene blue (824.87 mg/g) and iodine (2333.17 mg/g). Moreover, the cascade pyrolysis upgrading of AHL achieved a yield of 68.52% desired products, which was much higher than the reported results (single production of monophenols and pyrolysis char). In summary, this work provides a potential reference for efficient utilization of lignin in large-scale applications.