Sulfur-doped activated carbons (SACs) with high sulfur content and large specific surface area were synthesized from polythiophene for acetone removal. The sulfur content of carbons (3.10-8.43 at.%) could be tunable by adjusting the activation temperature. The BET surface area and pore volume of the obtained samples were 916-2020 m2 g-1 and 0.678-1.100 cm3 g-1, with a significant proportion of microporosity (up to 84% and 72% for BET surface area and pore volume, respectively). The resulting SACs show a superior acetone adsorption capacity (i.e., 716.4 mg g-1 at 15 °C and 705 mg g-1 at 25 °C for SAC700). In terms of the adsorption behavior of acetone on the activated carbons, compared to the Langmuir model, the Langmuir-Freundlich model showed better agreement with the adsorption amount. The results reveal that the surface area and micropore volume are the key factors for acetone adsorption, while the sulfur-doped functional groups, especially oxidized sulfur functional groups, can enhance the acetone adsorption capacity at a certain low pressure. Temperature programmed desorption (TPD) experiments were performed to get desorption activation energy of acetone on SAC samples, and the results ranged from 23.54 to 38.71 kJ mol-1. The results of the molecular simulation show that the introduction of sulfur element can increase the binding energy between acetone molecule and carbon surface, and the tri-oxidized sulfur (sulfonic acid) functional group has the highest binding energy of - 0.4765 eV. Graphical abstract.