Mesocarbon microbeads (MCMBs) were fabricated from coal tar pitches via the general air oxidization method. To track and analyze the structures of MCMBs in detail, air oxidization was carried out slowly. Polycondensation among the aromatic rings of polycyclic aromatic hydrocarbons in coal tar pitches is carried out mainly through the bonding type of Ar-R-O-R-Ar, which was verified by FT-IR measurements. Meanwhile, the lamellar structure is observed at the initial forming stage of the MCMBs, which was verified by measurements of X-ray diffraction. These results show that controlling the reaction condition is likely to fabricate MCMBs suitable for storage of lithium ions.