A novel fluorescent probe (C460@Tb-MOFs) was designed and synthesized by encapsulating the fluorescent dye 7-diethylamino-4-methyl coumarin (C460) into a terbium-based metal–organic framework using a simple ultrasonic impregnation method. It is impressive that this dye-modified metal–organic framework can specifically detect styrene and temperature upon luminescence quenching. The sensing platform of this material exhibits great selectivity, fast response, and good cyclability toward styrene detection. It is worth mentioning that the sensing process undergoes a distinct color change from blue to colorless, providing conditions for the accurate visual detection of styrene liquid and gas. The significant fluorescence quenching mechanism of styrene toward C460@Tb-MOFs is explored in detail. Moreover, the dye-modified metal–organic framework can also achieve temperature sensing from 298 to 498 K with high relative sensitivity at 498 K. The preparation of functionalized MOF composites with fluorescent dyes provides an effective strategy for the construction of sensors for multifunctional applications.