BACKGROUND: A series of hypercrosslinked resins were synthesized by controlling the reaction conditions of the Friedel-Crafts reaction of chloromethylated polystyrene-co-divinylbenzene (St-DVB-Cl), which realized reasonable adjustment of pore structure, surface area and other physical properties. Based on this, a new N,O modified hypercrosslinked resin (St-DVB-NB-AC(2)O) was successfully prepared by the innovative nitration system, and the adsorption behavior of St-DVB-NB-AC(2)O was studied under different conditions. The adsorption mechanism between adsorbent and adsorbate was explained by frontier orbital theory and density functional theory. RESULTS: The adsorption capacity of polyphenols on the optimal hypercrosslinked resin (St-DVB-NB-5) was 16.67% higher than that of the optimal commercial resin NDA150. Compared with St-DVB-NB-5, the adsorption increment of hydroxyphenol on St-DVB-NB-AC(2)O was 31.42%, which was 1.51-8.36 times higher than commercial materials. The Freundlich model was the most suitable for fitting the equilibrium data. However, the pseudo-first-/second-order rate equation was more appropriate for characterizing the kinetic data, suggesting that the adsorption process might be concerned with a physical reaction. CONCLUSION: The fundamental reason for the large adsorption capacity and fast adsorption rate of St-DVB-NB-AC(2)O is its strong physical structure and chemical surface properties, which provided improved guidance for the harmless and resource-based treatment of phenolic wastewaters. (c) 2018 Society of Chemical Industry