An amphiphilic pyrene derivative exhibiting unusually stable excimer emission due to strong aggregation is presented. The aggregated system served as an intelligent sensor for metal ions and nitro explosives in aqueous media. The excimer displayed excellent selectivity toward Cu2+ among the tested cations. The observation was interpreted on the basis of chelation of metal ions involving the hydroxyl and amino groups of two molecules, leading to the ligand-to-metal charge-transfer (CT) process. The excimer was further applied for the cell imaging of Cu2+ ions. Also, while treating the excimer with various nitro explosives, it displayed efficient 2,4,6-trinitrophenol sensing, corroborating mainly the CT process from pyrene to the analyte due to intercalation of the analyte within pyrene.