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The fundamental understanding of metal-organic frameworks (MOFs) is crucial since the relationship between the macroscopic properties of these materials and their molecular-level structures allows for the development of technological applications and improvements in current performance. The metal centers and attached functional groups dictate MOFs' dynamics, structure, and porosity. The development of the solid-state nuclear magnetic resonance (SSNMR) technique, capable of providing atomic-level information, enables the non-destructive characterization of the structure and dynamics of MOFs have become essential step in ameliorating our understanding and are often complementary to traditional methods. This review aims to briefly introduce the concepts of SSNMR and the methods employed when investigating the dynamics, structure, and mapping of functional groups of microporous materials, including MOFs. This review highlights the best experimental practices when working with these complex systems. The article scrutinizes the information on framework structures, active center, surface position, host-guest interaction, and intermediate interaction through different SSNMR spectrums. Despite all the recent technological advancements, the SSNMR still faces the challenges of large sample quantities, long experimental measurements and data analyses, and complex isotopic labeling, which are enlightened in this review.