Abstract: Metal-organic frameworks (MOFs) are a class of porous materials formed with metal ions or oligonuclear metallic complexes and organic ligands. MOFs have a wide range of applications in energy, environment and biomedicine areas due to their high specific surface area, high porosity, excellent thermal stability, etc. Mass spectrometry (MS) can efficiently identify specific metal species and precisely characterize compound composition, and its high sensitivity and fast analysis speed make it one of the effective methods for characterizing MOFs. In mass spectrometry, ionization of MOFs is an important prerequisite for mass spectrometric analysis and detection. Starting from the principles and characteristics of common ion sources, ion source, sample requirement and types of ions generated for characterizing MOFs by MS are summarized. Furthermore, the associated qualitative analysis, reaction monitoring and applications research of MOFs by MS are reviewed.