A light brown needle-like crystal of Mn-based metal–organic framework (MOF); [Mn2.5(µ3-OH)(DTDB)2], (DTDB = 2,2′-dithiodibenzoate), compound 1, was synthesized using hydrothermal technique. Compound 1 was systematically characterized by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), and infrared spectroscopy (IR). Photoluminescence study of compound 1 in an aqueous medium showed intense blue emission centred at 395 nm upon excitation at 310 nm. This emissive property of compound 1 was utilized for selective and sensitive detection of 2,4,6- trinitrophenol (TNP), 2,4- dinitrophenol (DNP) and 4-nitrophenol (NP) in the aqueous medium through luminescence quenching mechanism. As indicated by the good overlap of the absorption spectra of the analytes and the emission spectrum of the compound 1, and manifested as the reduction in luminescence lifetimes, it can be concluded that the resonance energy transfer is the most significant factor for the selective detection of aromatic nitro-phenol compounds. The resonance energy transfer requires the proximity of the donor and acceptor, which was achieved by the molecular level interactions between the ‘S’ atom of the DTDB ligand and phenolic –OH groups of the nitrophenols through non-covalent type interactions like hydrogen bonding and dipolar type interactions. Detection limits for TNP, DNP, and NP with the values of 208 ppb, 156 ppb, and 556 ppb, respectively, were obtained in an aqueous medium. The studies indicate that compound 1 could be helpful for detecting nitrophenol derivatives in water.