A series of Bi3+/Eu3+ co-doped Ca2Ta2O7 (CTO:Bi3+/Eu3+) phosphors were prepared by high-temperature solid-state method for dual-emission center optical thermometers and white light-emitting diode (WLED) device. By modulating the doping ratio of Bi3+/Eu3+ and utilizing the energy transfer from Bi3+ to Eu3+, the tunable color emission ranging from green to reddish-orange was realized. The designed CTO:0.04Bi3+/Eu3+ optical thermometers exhibit significant thermochromism, superior stability, and repeatability, with maximum sensitivities of Sa = 0.055 K-1 (at 510 K) and Sr = 1.298% K-1 (at 480 K) within the temperature range of 300-510 K, owing to the different thermal quenching behaviors between Bi3+ and Eu3+ ions. These features indicate the potential application prospects of the prepared samples in visualized thermometer or high-temperature safety marking. Furthermore, leveraging the excellent zero-thermal-quenching performance, outstanding acid/alkali resistance, and color stability of CTO:0.04Bi3+/0.16Eu3+ phosphor, a WLED device with a high Ra value of 95.3 has been realized through its combination with commercially available blue and green phosphors, thereby demonstrating the potential application of CTO:0.04Bi3+/0.16Eu3+ in near-UV pumped WLED devices.