(E)-N'-((2-Hydroxynaphthalen-1-yl)methylene)picolinohydrazide (H-PNAP) shows aggregation-induced emission (AIE) strictly in a 90% water/MeOH (v/v) mixture at 540 nm, and the solid-state emission is blue-shifted to 509 nm upon excitation at 400 nm. The AIE activity of H-PNAP is selectively quenched by 2,4,6-trinitrophenol (TNP) and 2,4-dinitrophenol (DNP) out of different nitroaromatic compounds with a limit of detection (LOD) of 7.79 × 10-7 and 9.08 × 10-7 M, respectively. The probe is nonemissive in aqueous medium (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, HEPES buffer, pH 7.2); however, it shows a strong emission to Al3+ (λem, 490 nm) in the presence of 17 other biological metal ions, and the LOD is 2.09 nM which is far below the WHO recommended value (7.41 mM). The emission of the [Al(PNAP)(NO3)2] complex is quenched by HF2 - (F- and PO4 3- are weak quencher), and the LOD is as low as 15 nM. The probable mechanism of the sensing feature of the probe has been authenticated by 1H nuclear magnetic resonance titration, mass spectrometry, Fourier transform infrared spectroscopy, Benesi-Hildebrand plot, and Job's plot in each case. The probe has some practical applications such as recovery of Al3+ from the drinking water sample, construction of the INHIBIT logic gate, and detection kits for Al3+ and TNP/DNP by simple paper test strips. The probe, H-PNAP, has successfully been applied to the detection of intracellular Al3+ and HF2 - ions in the human breast cancer cell, MDA-MB-468.