An unexpected recognition of β-cyclodextrin (CD) from α- and γ-CDs was achieved. The emission from a diboronic acid-containing tetraphenylethene (TPEDB) was amplified upon addition of β-CD, whereas there was almost no response for α-, and γ-CDs. TPEDB is proposed to be anchored onto the wide rim of β-CD through the alternative and conceptually new cooperative boronic acid/diol dynamic binding interaction, resulting in the restriction of intramolecular rotations of its phenyl rings (see scheme). © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.