The special polycylic cage structure of the typical third-generation energy-containing material hexanitrohexaazoisowoodsane （CL-20） makes its production process accompanied by high concentration of organic solvents， which has large biological toxicity. In order to solve the serious pollution emission caused by CL-20 production. A combined internal electrolysis-alkaline hydrolysis-biodegradation process was proposed. Firstly， nitro compounds were reduced by zero-valent. Ethyl acetate and chloroform could be decomposed to small molecular organic acids by alkaline hydrolysis. Then， organic pollutants in wastewater were removed by anaerobic-aerobic biological combination process. The results indicated that CL-20 in the wastewater was thoroughly removed at the optimal reaction pH of 2. For alkaline hydrolysis process， the optimal pH value and treatment time was found to be 11.0 and 4 h， respectively. The removal efficiencies of ethyl acetate and chloroform reached （99.4±0.1）% and （95.4±0.9）%， respectively. Biodegradability could be improved by internal electrolysis-alkaline hydrolysis pretreatment. The chemical oxygen demand （COD） in effluent could be as low as 300 mg·L^-1 during the integrated biological process of upflow anaerobic sludge reactor （UASB） and biological aerated filter （BAF）. The combined internal electrolysis-alkaline hydrolysis-biodegradation process offers bright prospects for the treatment of wastewater from the manufacture of CL-20.