Various materials have been developed to capture volatile organic compounds (VOCs) to mitigate air pollution. However, sorbent materials with excellent resistance to water are rare. Here, several Fe/N-doped activated carbons (ACs) have been prepared to capture VOCs in humid environments. The ACs were analyzed by various characterization techniques, such as BET, SEM, XPS, XRD, FTIR, and Raman. The results showed that Fe/N doping resulted in the specific surface area of the ACs increasing by 500 to 1000 m2g-1, the average pore size increasing to approximately 2nm, improved mesoporous structure, higher graphitization, lower hydrophilicity, and polarity. The VOCs adsorption performance of the ACs was evaluated by static and dynamic adsorption experiments. The uptake of toluene and ethyl acetate by ACs was enhanced to 224mgg-1 and 135mgg-1, respectively. And ACs were able to maintain 70 to 80% VOCs adsorption capacity for VOCs at 80% relative humidity. Furthermore, the microscopic mechanisms were investigated by the grand canonical Monte Carlo method (GCMC). The highly graphitized structure and the N functional groups favored the VOC adsorption process and discouraged the adsorption of water vapor. This work affirmed the dominance of Fe/N-doped carbon, which will contribute to the evolution of water-resistant VOCs adsorbent materials.