Large mesopores cellular foam (LMCFs) materials were synthesized using microemulsion templating in acidic solutions. The amine functional groups were attached to channels of LMCFs materials via post-synthesis grafting. The structural and chemical properties of these prepared materials were characterized by TEM, XRD, FTIR and nitrogen adsorption. These resulting materials had disordered mesopores with well-defined large mesopore. The bovine serum albumin (BSA) and glucose oxidase (GOx) were used for adsorption experiment. The biomolecule was immobilized by covalently couple to the interior surface of amino-functionalized mesostructured cellular foams (AF-MCFs). The results showed that AF-MCFs had high-capacity bioimmobilization ability.