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Fabrication of highly stable, reversible, and efficient portable sensors for the detection of explosives for safety and security is challenging due to the robustness of the currently available detection tools, limiting their mass deployment to the explosion prone areas. This paper reports a new direction towards the sensing of nitro- and peroxide-based explosives using highly stable rare-earth-doped BaWO4 nanofibers with remarkable sensitivity and reversibility. BaWO4 nanofibers doped with Tb3+ and Eu3+ ions are fabricated through a sol–gel electrospinning process, and their emission characteristics and application as a fluorescent probe for the sensing of 2-nitrotoluene and H2O2, explosive taggants representing a broad class of explosives, are studied in detail. Scheelite structured BaWO4 nanofibers exhibit excellent luminescence characteristics, and the rare-earth ion doping in the polycrystalline BaWO4 …