A novel “on–off” Al³⁺ ions fluorescence-enhanced sensor (E)-1-(((2-hydroxyphenyl) imino)methyl)naphthalen-2-ol (AH-2) and its hydrogel hybrid (PAMN) were synthesized. AH-2 showed excellent selectivity and ultrasensitive to Al³⁺ ions; the detection limit was 2.36 × 10^–9 M. The most plausible complexation mechanism was studied by ¹H NMR, FT-IR, HR-MS, Job’s plot and theoretical calculation. And, it was interesting that PAMN could adsorb Al³⁺ ions with a removal rate of over 99%, which also could easily be distinguished by the naked eye in UV lamp (365 nm). Before and after adsorption of Al³⁺ ions, the microstructures of PAMN were analyzed by scanning electron microscope and X-ray energy spectrometer. The silica gel detect plates prepared in this work could rapidly and conveniently detect Al³⁺ ions with a concentration greater than 5 × 10^–6 M (0.13 mg/L) in aqueous solution, and the detection concentration (0.13 mg/L) was lower than the national standard concentration of Al³⁺ ions (0.2 mg/L) in city tap water of china.