| Summary: | The development and utilization of 3p-block based MOFs as fluorescent materials has attracted significant attention in recent years. Herein, we have successfully constructed a versatile luminescent Ga-MOF (SNNU-63) with a 3d<sup>10</sup> configuration and a large ligand twist configuration. Interestingly, the as-synthesized Ga-MOF exhibits excellent luminescence property and a good material for blue light-emitting diode (LED). At 80 K, this Ga-MOF shows multi-emission centers at 381, 462, and 494 nm. As a ratiometric thermometer, this Ga-MOF exhibits an excellent temperature sensing property with high relative sensitivity (<i>S</i><sub>m</sub> = 2.60 % K<sup>−1</sup> at 110 K). The fluorescence intensity ratio <i>I</i><sub>381</sub>/<i>I</i><sub>494</sub> shows a very good fit for the Boltzmann results (80–240 K). Moreover, the luminescent Ga-MOF exhibits an excellent selective detection of Fe<sup>3+</sup> over other metal ions in aqueous an medium, and the limit of detection (LOD) towards Fe<sup>3+</sup> ions is calculated to be 1.227 × 10<sup>−4</sup> M. This work presents a versatile luminescent Ga-MOF material as a blue LED and fluorescent probe for low-temperature and selective Fe<sup>3+</sup> sensing.
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