Luminescence of porous coordination polymers (PCPs) or metal–organic frameworks (MOFs) is sensitive to the type and concentration of chemical species in the surrounding environment, because these materials combine the advantages of the highly regular porous structures and various luminescence mechanisms, as well as diversified host‐guest interactions. In the past few years, luminescent MOFs have attracted more and more attention for chemical sensing of gas‐phase analytes, including common gases and vapors of solids/liquids. While liquid‐phase and gas‐phase luminescence sensing by MOFs share similar mechanisms such as host‐guest electron and/or energy transfer, exiplex formation, and guest‐perturbing of excited‐state energy level and radiation pathways, via various types of host‐guest interactions, gas‐phase sensing has its unique advantages and challenges, such as easy utilization of encapsulated guest luminophores and difficulty for accurate measurement of the intensity change. This review summarizes recent progresses by using luminescent MOFs as reusable sensing materials for detection of gases and vapors of solids/liquids especially for O₂, highlighting various strategies for improving the sensitivity, selectivity, stability, and accuracy, reducing the materials cost, and developing related devices.

Reversible chemisorption of CO₂is realized by introducing monodentate hydroxide onto the pore surface of metal–organic frameworks.

Hydrazine can be grafted in CPO-27-Mg/MOF-74-Mg to provide an ultrahigh concentration of amine groups on the pore surface, giving an exceptionally high CO ₂ capture performance, especially at extremely low pressures.

A porous metal azolate framework [Zn(mpba)] (MAF-X8, H₂mpba = 4-(3,5-dimethylpyrazol-4-yl)benzoic acid) with large, hydrophobic, one-dimensional channels and good thermal/chemical stability was synthesized and characterized. High-quality MAF-X8 thin films were grown on stainless-steel fibers for solid-phase microextraction (SPME), which showed high sensitivity and selectivity towards non-polar volatile organic compounds.