The properties of surface plasmons are notoriously dependent on the supporting materials system. However, new capabilities cannot be obtained until the technique of surface plasmon enabled by advanced two-dimensional materials is well understood. Herein, we present the experimental demonstration of surface plasmon polaritons (SPPs) supported by single-layered MXene flakes (Ti 3 C 2 T x ) coating on an optical microfiber and its application as an ammonia gas sensor. Enabled by its high controllability of chemical composition, unique atomistically thin layered structure, and metallic-level conductivity, MXene is capable of supporting not only plasmon resonances across a wide range of wavelengths but also a selective sensing mechanism through frequency modulation. Theoretical modeling and optics experiments reveal that, upon adsorbing ammonia molecules, the free electron motion at the interface between the SiO 2 microfiber and the MXene coating is modulated (i.e., the modulation of the SPPs under applied light), thus inducing a variation in the evanescent field. Consequently, a wavelength shift is produced, effectively realizing a selective and highly sensitive ammonia sensor with a 100 ppm detection limit. The MXene supported SPPs open a promising path for the application of advanced optical techniques toward gas and chemical analysis.