The design and synthesis of sensitive and selective luminescent materials as chemical sensing agents is a fundamental goal in fluorescence assays. Considering high porosity, large surface area, excellent photoluminescence property of metal-organic frameworks (MOFs), luminescent properties of a microporous azine-functionalized MOF, TMU-16, dispersed in different metal ions and solvents have been investigated systematically. The TMU-16 displays superb luminescence emission, and it can detect Fe(III) and Cd(II) ions with high selectivity, excellent sensitivity, and short response time (<1 min). The emission intensities of TMU-16 were quenched upon the addition of Fe(III) and increased upon the addition of Cd(II). The effect of other metal ions on the fluorescence intensity of the MOF was also studied and other metal ions showed low interference response in recognition of Fe(III) and Cd(II). More importantly, this is the first example of MOF-based luminescent sensor as efficient multifunctional fluorescence material which can use for selective sensing of Fe(III) and Cd(II) ions and small molecules such as CH₂Cl₂.