This paper reports an inverted opal fluorescence chemosensor for the ultrasensitive detection of explosive nitroaromatic vapors through resonance-energy-transfer-amplified fluorescence quenching. The inverted opal silica film with amino ligands was first fabricated by the acid-base interaction between 3-aminopropyltriethoxysilane and surface sulfonic groups on polystyrene microsphere templates. The fluorescent dye was then chemically anchored onto the interconnected porous surface to form a hybrid monolayer of amino ligands and dye molecules. The amino ligands can efficiently capture vapor molecules of nitroaromatics such as 2,4,6-trinitrotoluene (TNT) through the charge-transfer complexing interaction between electron-rich amino ligands and electron-deficient aromatic rings. Meanwhile, the resultant TNT-amine complexes can strongly suppress the fluorescence emission of the chosen dye by the fluorescent resonance energy transfer (FRET) from the dye donor to the irradiative TNT-amino acceptor through intermolecular polar-polar resonance at spatial proximity. The quenching response of the highly ordered porous films with TNT is greatly amplified by at least 10-fold that of the amorphous silica films, due to the interconnected porous structure and large surface-to-volume ratio. The inverted opal film with a stable fluorescence brightness and strong analyte affinity has lead to an ultrasensitive detection of several ppb of TNT vapor in air.