Macroporous foams having 80 vol % of nominal porosity were synthesized by the copolymerization crosslinking of glycidyl methacrylate (GMA) based high internal phase emulsions (HIPEs). To alter the mechanical and thermal properties, cellulose nanocrystals (CNCs) were used as filler. For this purpose, CNCs were added to the continuous oil phase during emulsification process at a loading rate of 1, 5 or 7 wt %. Consequently, composite foams were obtained by purification of the polymerized HIPEs (polyHIPEs). The effect of CNCs on the morphological and mechanical properties was investigated. It was found that CNCs have a significant influence on the thermal stability and the compressive strength of the obtained foams. In the end, the neat polyHIPE foam and the polyHIPE/CNC composite foam with 1 wt % of CNC were post-functionalized by reacting phenylimidazole (PIAL) with the epoxy ring of the GMA units. Resulting amine functional foams and the neat foam were utilized in Cr(III) removal from aqueous solutions. It was demonstrated that amine functional foams have a great potential as sorbent materials. The results also showed that the existence of CNCs decreased the performance for removing Cr(III) ions. Nevertheless, functionalization by PIAL significantly improved the selectivity of Cr(III) in comperasion with the neat polyHIPE foam.