Reported herein is a sensitive and selective array-based sensing strategy based on differential interactions with three supramolecular cyclodextrin–fluorophore sensors. Each interaction results in a distinct fluorescence modulation response, and linear discriminant analyses of these responses results in 100% successful classification of three classes of isomeric analytes and two classes of analogous analytes. Calculated limits of detection for this system are at or near literature-reported levels of concern.