Abstract The explicit roles of the hardly avoidable oxygen species on carbon materials in various fields remain contentious due to the limitations of characterization techniques, which lead to a lack of fundamental understanding of carbon surface chemistry. This study delves exhaustively into the comprehension of the features of different oxygen‐modified carbons through the dynamic evolution of surficial oxygen functional groups. Significant differences of thermal stability and electronic properties among various oxygen species are elucidated via in situ characterizations and theoretical calculations, providing a reliable benchmark for identifying oxygen functional groups on carbon materials. The chemical properties of the carbon materials are simultaneously investigated to show the influence of the oxygen functional groups on carbon structures, redox stability, and scalable metal adsorption. These findings not only consider the common misconception that oxygen species produced under various conditions possess identical properties but also raise awareness of understanding carbon surface chemistry in the atomic level.