The rapid development of advanced material science boosts novel chemical analytical technologies for effective pretreatment and sensitive sensing applications in the fields of environmental monitoring, food security, biomedicines, and human health. Ionic covalent organic frameworks (iCOFs) emerge as a class of covalent organic frameworks (COFs) with electrically charged frames or pores as well as predesigned molecular and topological structures, large specific surface area, high crystallinity, and good stability. Benefiting from the pore size interception effect, electrostatic interaction, ion exchange, and recognizing group load, iCOFs exhibit the promising ability to extract specific analytes and enrich trace substances from samples for accurate analysis. On the other hand, the stimuli response of iCOFs and their composites to electrochemical, electric, or photo-irradiating sources endows them as potential transducers for biosensing, environmental analysis, surroundings monitoring, etc. In this review, we summarized the typical construction of iCOFs and focused on their rational structure design for analytical extraction/enrichment and sensing applications in recent years. The important role of iCOFs in the chemical analysis was fully highlighted. Finally, the opportunities and challenges of iCOF-based analytical technologies were also discussed, which may be beneficial to provide a solid foundation for further design and application of iCOFs.