The substantial energy consumption and carbon loss associated with conventional thermal regeneration of activated carbon (AC) pose significant constraints on the advancement of deactivated AC recycling. Here, a vacuum-thermal process was applied to regenerate AC saturated with VOCs. Results showed that desorption efficiency under vacuum conditions (99 % at 200 °C) was significantly higher than that in air and nitrogen (85.2 % and 86.4 %, respectively). The adsorption capacities of different AC samples were maintained at 74.2 %, 97.8 %, 90.9 %, and 96.4 % after seven regeneration cycles, respectively. Pore structure analysis showed that vacuum-thermal regeneration caused less damage to the AC pore structure compared to the air and nitrogen. In addition, micropores were shown to be most conducive to the adsorption of VOCs, while mesopores larger than 4 nm are conducive to desorption. The larger the saturated vapor pressure of the VOCs, the larger the driving force it is subjected to, and the easier it is to desorption. Density field theory (DFT) calculations showed that the higher the binding energy between VOCs and AC surface, the more stable the adsorption system, making it more difficult to regenerate the adsorbent. This work provides insight into the development of an economical and environmentally friendly regeneration route for AC adsorption.