As the limiting factor for an energy storage technique from lab‐scale to industrial‐scale, cost means not only the price of raw materials but also the simplicity of processing technics. In this work, the oxygen functionalized carbon materials were obtained from three representative different metamorphic‐grade coals, that is, lignite, bitumite, anthracite. Oxygen functional groups like quinones, carboxylic anhydrides, and lactones are easier to form near defects according to the thermogravimetric‐mass spectrometry measurements and density functional theory calculation. Considering the highest amount of defects and C=O contained functional groups, the low metamorphic‐grade lignite derived carbon exhibits a reversible capacity of 259.7 mA h g⁻¹ after 50 cycles at 0.03 A g⁻¹, best among these micron sized coal‐based carbons. The surface active sites contribute highly stable and majority of sodium storage capacity evidenced by in situ Raman spectra and cyclic voltammetry curves at different scan rates. The coal‐based carbon materials in this work offer options for industrial applications of sodium‐ion battery anode materials.

The addition of CaO to the CeO ₂ catalyst had a significant impact on the acid–base properties and amounts of oxygen vacancies on the surface catalyst.