The quantitative measurement of adsorbed guest species within Metal‐organic framework (MOF) pores is of fundamental importance for evaluating the adsorption performance of MOFs. However, routine analytic techniques such as thermogravimetric analysis cannot distinguish the contribution from species adsorbed within pores, species adsorbed on the surface, and gas phase or liquid phase encapsulated in the inter‐crystalline space. Herein, we developed a new quantification method based on the cross‐polarization (CP) solid‐state nuclear magnetic resonance (SSNMR) technique, in which only the species within MOF pores are selectively probed due to the dramatically reduced mobility. Using the commercialized MOF α‐Mg3(HCOO)6 as an example, a good linear correlation between Areaguest/Areaframework (i.e., the integrated area of guest and framework 13C NMR signals, respectively) and guest loading can be observed for several representative molecules such as benzene, tetrahydrofuran (THF), and 1,4‐dioxane, clearly revealing the feasibility of CP quantification approach. The effects of guest molecule and corresponding residual mobility on the CP quantification are further discussed by varying the geometry and size of guest molecules. This methodology thus provides an effective and irreplaceable route to evaluate the adsorption performance of porous materials in‐depth, especially for liquid‐phase adsorption and gas‐phase adsorption in which the capillary condensation is not negligible.