Abstract: In this work, to better understand catalytic gasification process of direct coal liquefaction residue rich in sodium species, char structure evolution and behaviors of sodium species during gasification under CO₂ atmosphere were investigated in detail by N₂ adsorption and desorption, FT-IR, XRD, SEM, and Raman analyses. The results show that sodium species developed pore structure of direct coal liquefaction residue during gasification, especially expanded mesoporous structures which increased from 0.05 to 0.16 cm³/g at maximum. With the increase of gasification time, different crystalline compounds were formed in chars. Most of the mineral matters identified by XRD were calcium-containing ones, whereas no obvious sodium-containing crystalline compounds were found. This was because that most of sodium species volatilized at high temperature and the crystalline forms of sodium-containing compounds had defects. Compared with sodium species, calcium species were more prone to react with aluminosilicates, which happened to make sodium species remain active during gasification process. The ratio of (G_R + V_L + V_R)/D rose initially and then decreased, which could be explained as the dissociation of the large aromatic and the rearrangement of small aromatic rings into large aromatic structures. Moreover, release ratio of sodium species was closely related with gasification time and 49.8% of them released in the initial stage of gasification process (within 15 min). Compared with that of direct coal liquefaction residue reloaded with water-soluble sodium species, the release ratio of sodium species in the original direct coal liquefaction residue was on a lower level (85.2% versus 89.7%).