In this chapter, the analysis of molecular motion in solid materials, which is connected with the function of those materials, using 2H NMR spectroscopy is described. The line shape of a 2H NMR spectrum, which is dominated by the quadrupole interaction, is very sensitive to molecular motion. The mode and rate of molecular motion in the dynamic range of 104~107 Hz can be obtained by the line shape analysis of a 2H NMR broad line spectrum of a powder sample using spectral simulation. Molecular motion in the order of 103 and 108 Hz can be analyzed by a line shape and line width of a 2H NMR Quadrupolar Carr-Purcell-Meiboom-Gill (QCPMG) spectrum. The analysis of molecular motion in paramagnetic materials is possible by simulation of the 2H NMR spectrum, including paramagnetic effects. The methods used to simulate these spectra are explained. In addition, the application of these methods to porous coordination polymer (PCP)/metal–organic framework (MOF), proton conducting material, and spin-crossover material is introduced.