Metal‐organic frameworks (MOFs) are a novel type of porous materials with many current and potential applications. Solid‐state NMR (SSNMR) spectroscopy is an excellent technique for MOF characterization. It can provide nuclide‐specific information on structure and dynamics, which is complementary to that obtained from X‐ray diffraction. The NMR‐active isotopes of vast majority of metal centers including
27
Al,
71
Ga,
45
Sc,
67
Zn,
25
Mg, and
115
In as well as some framework elements such as
17
O are quadrupolar nuclei. Compared to
spin
‐1/2 nuclei such as
13
C, SSNMR spectroscopy of quadrupolar nuclei has traditionally considered very challenging because of the quadrupolar interaction that makes spectral acquisition and interpretation difficult. This is particularly true for those so‐called unreceptive quadrupolar nuclei (i.e., the nuclei with low gyromagnetic ratios, low natural abundances, and large quadrupole moments). However, in recent years, significant progresses have been made in developing SSNMR spectroscopy of quadrupolar nuclei. This chapter begins with a brief introduction of NMR spectroscopy of quadrupolar nuclei; followed by discussion of several very recent examples to illustrate that SSNMR spectroscopy of quadrupolar nuclei can be used as an effective tool to characterize the nuclear environments in MOF‐based materials. It is hoped that this chapter will encourage more researchers to use SSNMR spectroscopy for investigation of MOF properties by interrogating quadrupolar nuclei.