Two negatively charged species of silica nanoparticles and exfoliated clay nanosheets have been successfully assembled into highly porous frameworks through a direct hybridization reaction with the help of a surface modification technique. In order to create attractive Coulombic interaction between two components, the surface of silica was modified with positively chargeable aminosilane coupling agents. Without any additional post-calcination, as-prepared hybrid materials are highly porous with the BET specific surface area of 480 m(2)/g.