Carbon is a unique and versatile element in nature that can form different architectures. Heteroatom (e.g., B, N, O, P, and S) modification has been proven to be an effective way to tailor the chemical and electrical properties of the carbon surface. Moreover, nanocarbons have been reported to be good supports for metal nanoparticles (NPs). It is essential to study the metal–support interaction between surface‐modified carbon and metal NPs to understand performance. Advanced analytical transmission electron microscopy techniques are powerful tools that can be used to probe the metal–carbon support interaction in carbon‐supported metal catalysts, as they can directly uncover local structures of the surface and the bulk of catalysts at the atomic scale and can also reveal chemical and electronic structural information that is related to their synthesis and catalytic properties significantly affecting their performance. Herein, several selected examples will be reviewed.