A polyamine functionalized polystyrene resin (PSATA) was prepared via condensation reaction of acetylated polystyrene resin with triethylenetetramine, which, upon NaBH4 reduction, produced PSATAR. In comparison with the PSATA, the PSATAR with more flexible amine groups shows improved structural properties, and the equilibrium adsorption capacities of phenol, 2-nitrophenol (ONP) and 2,4-dinitrophenol (DNP) in wastewater were up to 1.073, 1.832 and 1.901 mmol/g, respectively. Their adsorption isotherms fit well with the Freundlich model, indicating a multilayer, heterogeneous adsorption nature. Kinetic studies indicated that the adsorption of phenolic compounds conforms to the pseudo-second-order kinetics with the adsorption rate controlled by film diffusion for ONP and DNP, and intra-particle diffusion in the later stage for phenol.