Chlorophenols (CPs), a kind of important intermediate for fine chemicals, exists widely in the aqueous environment and poses a significant danger to humans. Therefore, developing advanced materials to enable the effective capture of CPs is highly desired. Herein, β-cyclodextrin-based porous carbon (CPAC) with exceptional capacities for CPs has been designed and tested. These porous carbon adsorbents were successfully synthesized via stepwise carbonization, affording abundant N and O functional groups, high surface area (as high as 3982 m2·g−1) and controlled pore size to optimize for rapid CPs uptake. According to the CPs uptake measurements, CPAC exhibited exceptional CPs adsorption performance. CPAC showed high adsorption capacities (1085.08 mg·g−1 for 2,4,6-trichlorophenol) and fast adsorption kinetics for CPs. CPAC can effectively recover multi-component CPs from complex aqueous media, and the special pore structure reduces the competitive adsorption between CPs. And the recyclability studies showed that CPAC maintained its structural integrity and the initial CPs uptake capacity, highlighting its potential for practical application. Besides, DFT calculations indicate that hydrogen bonding and π-π interactions are key factors. Among them, the molecular conformation of CPs and the number of chlorine atoms on phenol play a crucial role in the adsorption behavior and adsorption energy.