A new family of cyclic and acyclic BINOL-derived triazoles has been prepared for the organocatalytic silylation and subsequent use of fluorescent sensors, in which this type of receptor can unexpectedly recognize I− with good selectivity. The spectral analysis, including UV and NMR titrations, demonstrated that the anion–π interaction of I− to the triazole ring was responsible for the formation of a weak charge-transfer complex.