A novel multifunctional Pb(II)-based MOF, [Pb(DBPT)]·(DMA)(HO) (1), with excellent chemical stability, was successfully assembled by connecting {PbO} unit with a multi-topic polycarboxylate ligand of 3-(3,5-dicarboxylphenyl)-5-(4-carboxylphenyl)-1-H-1,2,4-triazole (HDBPT). It exhibits dual fluorescence emissions at 380 nm (λ = 280 nm) and 540 nm (λ = 380 nm), respectively. Through the adjustable dual fluorescence emissions, it could act as a turn-off and turn-on switch for detecting N,N-dimethylacetamide (DMA) molecule. Moreover, Fe ions exert luminescence quenching role on compound 1 at both excitation lengths in water, among which the quenching at λ = 280 nm is of high sensitivity (K = 1.2 × 10), and the quenching at λ = 380 nm is of wide-range. The sensing for metal ions of In, Zr, and Al is also effective at λ = 280 nm, with the K constants of 1.6 × 10, 1.6 × 10, and 4.3 × 10, respectively. More importantly, a series of nitroaromatic compounds (TNP, 2,4,6-trinitrophenol; 4-NA, 4-nitroaniline; NB, nitrobenzene) and nitro-based drugs (MNZ, metronidazole; DMZ, dimetridazole) could be detected at both excitation lengths, demonstrating the advantage of broad range response of fluorescence sensing. Thanks to the excellent chemical stability and unusual dual emission luminescence properties for chemical detection of various metal ions, nitro-based molecules and DMA solvent, the Pb-based MOF reported in this work is, therefore, a very promising multi-response sensor.