Aminated polystyrene resins (NDA-101 and NDA-103) were synthesized, and their adsorption performances for phenol in aqueous solutionwere investigated and compared with the commercial polystyrene resin (Amberlite XAD-4) andweakly basic polystyrene resin (Amberlite IRA-96). All the associated adsorption isotherms are well described by Freundlich and Langmuir equations. The results indicated that all the four resins spontaneously adsorb phenol driven mainly by enthalpy change, and their adsorption capacities, free energy changes, enthalpy changes, and entropy changes for phenol followed the same order as: NDA-101>NDA-103>XAD-4>IRA-96. Surface energy heterogeneity analysis by Do's model also suggested that the surfaces of XAD-4 and IRA-96 were more homogeneous, and the better adsorption capacity and affinity of the aminated resins (NDA-101 and NDA-103) are probably due to their multiple hydrogen bonding and-stacking interactions with phenol molecule.