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.