Nitroaromatic explosives pose a great threat to the environment and human safety. It is very important to design simple, highly efficient and multifunctional sensors for detecting nitroaromatic explosives. However, a few sensors can determine multicomponent nitroaromatic explosives simultaneously. Eu functionalized MOF-253 (Eu@MOF-253) hybrid material was synthesized using the post-synthetic modification method. The introduction of Eu3+ in MOF-253 caused the fluorescence peak of the ligand to show a distinct red-shift due to its polarization enhancement effect in the presence of 2,4-DNP. The emission and excitation spectra of the Eu@MOF-253 sensor showed overlap with the ultraviolet-visible (UV-vis) absorption spectra of the representative nitroaromatic explosives 2,4-dinitrophenol (2,4-DNP) and 2,4,6-trinitrophenol (TNP). Therefore, it is feasible to discriminate and quantify TNP and 2,4-DNP simultaneously. As proposed, the Eu@MOF-253 luminescent sensor was highly sensitive and selective towards TNP and 2,4-DNP. The other coexisting nitroaromatic explosives did not interfere with the determination. Upon addition of TNP, the fluorescence of the Eu@MOF-253 sensor decreased dramatically and showed an excellent quenching constant (Ksv) of 1.58 × 106. The fluorescence intensities of the Eu@MOF-253 sensor presented good linear relationships with concentrations of TNP and 2,4-DNP ranging from 0.01-100 μM and 0.01-25 μM, respectively. Low limits of detection (LOD) for both 2,4-DNP and TNP were approximately 10 nM. The determination mechanism is mainly ascribed to the internal filtration effect (IFE) and electron transfer. This work provides a practical method for the highly efficient determination of nitroaromatic explosives.