Microporous materials have attracted a rapid growth of research interest in materials science and the multidisciplinary area because of their wide applications in catalysis, separation, ion exchange, gas storage, drug release, and sensing. A fundamental understanding of their diverse structures and properties is crucial for rational design of high-performance materials and technological applications in industry. Solid-state NMR (SSNMR), capable of providing atomic-level information on both structure and dynamics, is a powerful tool in the scientific exploration of solid materials. Here, advanced SSNMR instruments and methods for characterization of microporous materials are briefly described. The recent progress of the application of SSNMR for the investigation of microporous materials including zeolites, metal-organic frameworks, covalent organic frameworks, porous aromatic frameworks, and layered materials is discussed with representative work. The versatile SSNMR techniques provide detailed information on the local structure, dynamics, and chemical processes in the confined space of porous materials. The challenges and prospects in SSNMR study of microporous and related materials are discussed.