A simple Schiff-base ligand 2-hydroxy-1-naphthaldehyde semicarbazone (HNS) was synthesized and characterized. Based on the combined effect of inhibition of CHN isomerization and chelation-enhanced fluorescence (CHEF), HNS functions as a fluorescence “turn on” sensor for Al³⁺ in buffered aqueous media. Based on the strong affinity of Al³⁺ to F⁻ ions, the in situ generated Al³⁺–HNS complex can also be utilized as an effective chemosensor for F⁻ sensing by metal displacement approach, ensuing quenching of fluorescence by the reversible return of HNS from Al³⁺–HNS complex. Thus a method using a single probe for the detection of both Al³⁺ and F⁻ ions is developed. The system exhibits high selectivity and sensitivity for Al³⁺ and F⁻ ions and the detection limits were found to be as low as 6.75 × 10⁻⁸ M and 7.89 × 10⁻⁷ M, respectively. Furthermore, the practical applicability of this probe has been examined in living cells.