Gas molecules and volatile compounds in the air affect product purity and health. Because of increasing demand for better quality of life and health in industrial and general environments, timely detection of abnormal gas releases and poisonous compound volatilization is essential. Luminescence metal-organic frameworks (LMOFs) are materials with tunable pore sizes, defined structures, and luminescence properties, which have been widely reported as sensor materials for detecting various compounds. Here, luminescence mechanisms of LMOFs are reviewed and interactions between the host and guest molecules are explained at the molecular level. On the basis of these relationships, the state-of-the-art LMOF-based sensors for various common gas molecules (including H2O, O-2, COx, and NOx) and volatile organic compounds (VOCs) are further described in depth. This review may benefit the further development of LMOFs and accelerate their practical application in various sensor combinations.