Single doped Mg0.388Al2O3.408O4 phosphor was prepared and multivalent Mn ion (Mn2+ and Mn4+) emission was achieved in a single host. The structure, morphology, and luminescence characteristics of Mn ions in Mg0.388Al2O3.408O4 were discussed in detail, especially the temperature dependent emission characteristics of Mn ions. Based on the fluorescence intensity ratio (FIR) of Mn2+versus Mn4+ and the decay lifetime of Mn4+ emission as the temperature readout, a dual-mode optical temperature-sensing mechanism was proposed and studied in the temperature range of 293–473 K. The maximum relative sensitivities (Sr) are derived as 2.83 % K−1 (at 373 K based on FIR) and 3.40 % K−1 (at 473 K based on decay lifetime), respectively. The temperature sensing characteristics of Mg0.388Al2.408O4: Mn2+/Mn4+ powders in a full fiber system were studied, which can provide thermal-sensitive emissions at dual-wavelengths for stable ratiometric temperature sensing with good precision and repeatability. The constructed all fiber temperature sensing system has been applied in the on-line monitoring of CPU temperature.