This article describes the preparation of pyrene confined mesostructured silica nanoparticles for the trace detection of trinitrotoluene (TNT) in the aqueous phase. Pyrene confined mesostructured silica nanoparticles were prepared using a facile one-pot method where pyrene molecules were first encapsulated in the hydrophobic parts of cetyltrimethylammonium micelles and then silica polymerized around these micelles. The resulting hybrid particles have sizes of around 75 nm with fairly good size distribution. Also, they are highly dispersible and colloidally stable in water. More importantly, they exhibit bright and highly stable pyrene excimer emission. We demonstrated that excimer emission of the particles exhibits a rapid, sensitive and visual quenching response against TNT. The detection limit for TNT was determined to be 12 nM. Furthermore, excimer emission of pyrene shows significantly high selectivity for TNT.