In the present study, the adsorptive potential of hypercrosslinked polymers (HCPs) was investigated for the removal of phenol from aqueous solutions. Herein, two HCPs were one-step synthesized by the Friedel-Crafts reaction using 4,4′-biphenyldiol (BPD) or hydroquinone (HQ) as the building unit and 1,4-bis(chloromethyl)benzene (DCX) as the external crosslinker. The results showed that the HCPs, derived from BPD and DCX (called as BPD-D), exhibited more excellent pore structures with the higher surface area of 697 m2 g−1 and the micropore volume of 0.23 cm3 g−1 and allowed for the extremely fast equilibrium adsorption of phenol, attributed to the hierarchical pore structure and the great hydrophilicity; meanwhile, the maximum adsorption capacity of BPD-D towards phenol was calculated to be 156.74 mg g−1. Moreover, the adsorption equilibrium and kinetic processes of BPD-D towards phenol were well described by the Freundlich model (R2 > 0.99) and the pseudo-second-order kinetic model (R2 > 0.9999) at 303 K. Moreover, negative changes in Gibbs free energy and enthalpy reflect that the adsorption of BPD-D for phenol is a spontaneous and exothermic process. In addition, adsorption performances were investigated under different conditions, e.g., the initial concentrations of phenol, the dosage of the BPD-D, the initial pH of phenol aqueous solution and recyclability. Our finding demonstrates that HCPs show potential application prospects in the removal of organic pollutants from wastewater.