NMR relaxometry has been widely applied to characterize fluid confined in porous media because of its versatility, chemical selectivity, and noninvasive nature. Here we extend its usage to gas adsorbed in microporous materials by establishing a new quantitative model based on the molecular level NMR relaxation mechanism revealed by the molecular simulation of a prototypical adsorption system, CH4 adsorbed in ZIF-8. The model enables new NMR relaxometry-based characterization methods for thermodynamic, dynamic, and structural properties of adsorption systems, as demonstrated and validated by the experiments where the adsorption capacity and self-diffusivity of H2, CH4, and small alcohols adsorbed in ZIF-8 are deduced from the NMR relaxation data. The findings can serve for a better understanding of the composition-structure-properties relationships of a wide range of adsorption systems which is essential for the development and application of new functional microporous materials.