The interplay of ESIPT+TICT mechanisms in 1,8-naphthalimide-hydroxyquinoline (NQ-OH) molecular rotor were reported for the near-IR 'turn-on' emission (λmax 600 nm) and ratiometric (A405nm/A345nm) absorbance-based detection of Al3+ ions in aqueous medium and live cells which were supported by NMR, IR and CV techniques. The limit of detection (LOD) for Al3+ ions is 100 nM and 14.57 nM. The self-assembled spherical aggregates of NQ-OH transformed into cuboidal aggregates upon coordination with Al3+ ions supported by microscopic and dynamic light scattering (DLS) techniques. The complex NQ-OH+Al3+ was further used for the secondary detection of F- ions in aqueous medium via displacement approach with LOD as low as 2.67 nM. A deeper study revealed that the NQ-OH is a solvatochromic dye. Probably, the NQ-OH either in the aggregated state or in the coordination state with Al3+ ions, showed an increase in the emission intensity at 600 nm due to inhibition of the ESIPT process and trigger of the TICT process. We have demonstrated the utility of NQ-OH for the detection of Al3+ ions and NQ-OH+Al3+ complex for the detection of F- ions in MCF7 live cells. We have also discussed the molecular docking studies of NQ-OH with acetylcholinesterase enzyme.