Convenience food products tend to alter their quality and texture while stored. Texture‐giving food components are often starch‐rich ingredients, such as pasta or rice. Starch transforms depending on time, temperature and water content, which alters the properties of products. Monitoring these transformations, which are associated with a change in mobility of the starch chain segments, could optimize the quality of food products containing multiple ingredients. In order to do so, we applied a simple and efficient in situ 13C solid‐state magic angle spinning (MAS) NMR approach, based on two different polarization transfer schemes, cross polarization (CP) and insensitive nuclei enhanced by polarization transfer (INEPT). The efficiency of the CP and INEPT transfer depends strongly on the mobility of chain segments—the time scale of reorientation of the CH‐bond and the order parameter. Rigid crystalline or amorphous starch chains give rise to CP peaks, whereas mobile gelatinized starch chains appear as INEPT peaks. Comparing 13C solid‐state MAS NMR experiments based on CP and INEPT allows insight into the progress of gelatinization, and other starch transformations, by reporting on both rigid and mobile starch chains simultaneously with atomic resolution by the 13C chemical shift. In conjunction with 1H solid‐state MAS NMR, complementary information about other food components present at low concentration, such as lipids and protein, can be obtained. We demonstrate our approach on starch‐based products and commercial pasta as a function of temperature and storage.