Development of energy and resource-efficient processes to convert sustainable agricultural and forestry waste into valuable platform compounds, such as 5-hydroxymethylfurfural (5-HMF), has become an important research area for promoting a bioeconomy. However, separation and purification of 5-HMF from hydrolysate is a major challenge for its large scale industrial production. In this work, a series of novel polar-modified post-cross-linked resins were synthesized by oil/water suspension polymerization, post-cross-linked, and amination reactions using different monomer/cross-linker ratios. Different mass percentages of toluene were also included as a porogen. The effect of pore structure on the equilibrium capacity of 5-HMF onto resins using both single and ternary-component systems was investigated. The results showed that the post-cross-linked resin with ethylene glycol dimethacry late/divinylbenzene (at 1:4 w/w) with 100% (w/w) toluene had the largest BET surface area (1075 m(2)/g). The largest 5-HMF equilibrium capacity was 65.8 +/- 1.3 mg/g in the single-component system and 57.9 +/- 1.3 mg/g in the ternary-component system. Additionally, the maximum selectivity values of 5-HMF-FA and LA-FA are 26.6 and 14.2 on PCL-PDE resin with the 100% toluene mass percentage. Furthermore, the average pore diameter and BET surface areas of the resin played a significant role in the adsorption process of 5-HMF from both single- and ternary-component systems. In all, this research provides an important theoretical and practical screening method for the directed design of adsorbents for 5-HMF separation and purification.