A novel mesoporous organosilica with additional cyclodextrin-based micropores has been synthesized from tetraethoxysilane (TEOS) and cyclodextrin-based silane monomer precursors and triblock PEO-PPO-PEO (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) copolymer P123 as the structure-directing template with the aid of sodium chloride and the supramolecular assembly of cyclodextrins with P123.