Abstract The study of carbonization and activation mechanism is essential for the preparation of high-performance biomass-based activated carbon (AC), which has been widely used in many fields. In this work, an online volatile analysis and real-time sampling was carried out to study the carbonization and activation mechanism of AC prepared by pyrolysis of Chinese parasol sawdust and ZnCl2 mixture. Combining a series of analysis results, it was found that the effect of ZnCl2 could be divided into three stages: (1) At low temperature ( O bonds in solid residues at 300−400 °C; (3) It catalyzed the aromatization reaction at temperatures ≥ 400 °C, and formed a large number of pore structures through the swelling effect of ZnCl2 and the release of small molecular gases. 2308 m2/g of micropore AC with micropore ratio of 71.9 % and 2057 m2/g mesoporous AC with mesoporous ratio of 58.6 % were obtained when the temperature just rose to 500 °C and 550 °C, respectively. No additional activation time was required, which helped to save time and energy consumption in AC production.