A supramolecular receptor consisting of two anthracene moieties with binding motifs for binding of benzoate anions is reported here. NMR studies indicate that the binding involves π–π interactions and CH⋯X interactions. Upon exposure to >350 nm light, the receptor undergoes a [4 + 4] photoelectrocyclization restricting the access to the binding site for benzoate. The reverse reaction works in the presence of the dual stimuli of 254 nm light and the benzoate anions. The work thus demonstrates a light mediated dynamic control of the binding pocket of a supramolecular anion receptor.