An aminated hypercrosslinked macroporous polymeric adsorbent was synthesized and characterized. Adsorption isotherms for 1-amino-2-naphthol-4-sulfonic acid(1, 2, 4-acid) and 2-naphthol obtained from various binary adsorption environments can be well fitted by Freundlich equation, which indicated a favorable adsorption process in the studied range. Adsorption for 1, 2, 4-acid was an endothermic process in comparison with that for 2-naphthol of an exothermic process. 2-naphthol molecules put a little influence on the adsorption capacity for 1, 2, 4-acid. However, the adsorption to 1, 2, 4-acid depressed that to 2-naphthol in a large extent for the stronger electrostatic interaction between 1, 2, 4-acid and adsorbent. The predominant mechanism can be contributed to the competition for adsorption sites. And the simultaneous environment was confirmed to be helpful to the selective adsorption towards 1,2,4-acid based on the larger selectivity index.