A novel amino modified hierarchically macro–mesoporous cross-linked polystyrene adsorbent (HP CLPS-EDA) was fabricated via the combination of colloidal crystal templating method with Friedel–Crafts (F-C) technique, and adsorption performance of salicylic acid (SA) from aqueous solutions on HP CLPS-EDA was investigated. Compared with the amino modified three dimensional ordered macroporous CLPS (3DOM CLPS-EDA), the HP CLPS-EDA showed the largest adsorption capacity towards SA and maximum utilization of amino groups. Furthermore, the adsorption characteristics of HP CLPS-EDA including adsorption isotherms, adsorption kinetic, effect of solution pH on adsorption and the regenerations performance were researched and discussed. It was shown that, the maximum adsorption capacity of HP CLPS-EDA predicted by the Langmuir model was much higher than the most adsorbents reported in literatures. Additionally, the adsorption capacity of HP CLPS-EDA towards SA was well retained in a wide range of solution pH. After fifteen times regenerations, over 95% of the initial adsorption capacity of HP CLPS-EDA was preserved and the morphology was well retained.