Multifunctional ratiometric and lifetime-technology dual-mode sensing plays a pivotal role in optical thermometry, yet poses substantial challenges in Mn4+-doped oxyfluorides/fluorides. Especially, despite of higher sensitivity, the applicability of lifetime-mode optical thermometers is generally restricted to large volume, highly integrated spectrometers. Here, a Mn4+-doped oxyfluoride single crystal Na2NbOF5:Mn4+ (NNOFM) is demonstrated as accurate dual-mode optical temperature sensor and developed into a portable optical fiber thermometric platform. Homogeneous NNOF shell is grown to improve the moisture resistant for extending operational lifespan. Under blue light excitation, two different temperature-sensitive sharp line vibrational transitions endow ratiometric mode temperature sensor. Importantly, rapidly decaying lifetime of Mn4+ produces high relative sensitivity Sr of 5.36 % K−1 at 448 K among Mn4+-based phosphors. Integrating NNOFM core–shell single crystal into optical fiber and coupling pulsed laser and oscilloscope, a portable optical fiber thermometric platform is realized. Accurate measurement result of boiling water being 373.33 K with quite small relative standard deviation to 0.04 % shows great potential of this fabricated thermometric platform for practical applications. This study not only enlightens the design of high-precision dual-mode optical thermometers in Mn4+-doped oxyfluorides/fluorides, but also illuminates the path to create portable optical fiber thermometric platforms.