The turn-on luminescent chemosensor [2-Hydroxy-1-naphthaldehyde-(2-pyridyl) hydrazone] (L), selective to Al 3+ ions, was studied by means of density functional theory (DFT) and time-dependent-DFT quantum mechanics calculations. The UV-Vis absorption and the radiative channel from the adiabatic S 1 excited state were assessed in order to elucidate the selective sensing mechanism of L to Al 3+ ions. We found that twisted intramolecular charge transfer (TICT) and photoelectron transfer (PET), which alter the emissive state, are responsible for the luminescence quenching in L. After coordination with Al 3+ , the TICT is blocked, and PET is no longer possible. So, the emission of the coordination complex is activated, and a fluorescence effect enhanced by chelation is observed. For compounds with Zn 2+ and Cd 2+ , the luminescence quenching is caused by PET, while for Ni 2+ , ligand to metal charge transfer is the prominent mechanism. To go into more detail, the metal-ligand interaction was analyzed via the Morokuma-Ziegler energy decomposition scheme and the natural orbital of chemical valence.