Due to the influence of the thermal quenching effect, the luminescence intensity of luminescent materials sharply decreases in high-temperature regions, strongly affecting their application in optical anti-counterfeiting and optical temperature supervision. In this study, we report a multi-mode anti-counterfeiting phosphor doped with Eu3+ that exhibits fluorescence thermoluminescence enhancement. This phosphor can trap electrons and release them as luminescence under external stimulation (the light and heat). The compensatory luminescence at high temperatures is the reason for the unique fluorescence thermoluminescence enhancement characteristics of this phosphor. Therefore, the sensitivity and differential response of this phosphor to light and heat can be used to monitor anti-counterfeiting patterns or temperature. This work provides an example for the future application of optical anti-counterfeiting and temperature monitoring.