A naphthylamide based fluorescent chemosensor, N,N′-(1,2-phenylene)bis(1-hydroxy-2-naphthamide) (H₄L), for detection of Fe³⁺ and Al³⁺ cations as well as CN⁻ anion is reported. This compound has been synthesized by a novel and facile synthetic method with high yield and characterized by FT-IR, ¹H NMR, elemental analysis, and UV–Vis spectroscopy. It could detect Fe³⁺ and Al³⁺ ions in different media with different excitation and emission wavelengths. In DMSO solution, H₄L showed selective ON-OFF quenching of its 451 nm emission in the presence of Fe³⁺. On the other hand, in DMF solution, H₄L exhibited selective OFF-ON fluorescence upon the addition of Al³⁺, the intensity at 429 nm increases drastically by 24-fold. Also, among the anions, the probe can selectively distinguish CN⁻ by deprotonation of OH and NH groups, as proved by ¹H NMR titration. TD-DFT calculation supports the UV–Vis …