Switchable β-cyclodextrin (β-CD)-induced hydrolysis of m-tert-butylphenyl acetate is demonstrated in the presence of supramolecular β-CD/adamantane oligonucleotide scaffolds. In one system, a duplex between a β-CD-functionalized nucleic acid and an adamantane-nucleic acid leads to a switchable catalytic system. In a second system, a β-CD/adamantane duplex is cooperatively generated by K(+)-stabilized G-quadruplex units. The binding of hemin to the second system yields a bifunctional DNA scaffold with alternate catalytic functions.