High crystallinity coke-based activated carbon (hc-AC) is prepared using a potassium hydroxide solution to adsorb carbon dioxide (CO2). The CO2 adsorption characteristics of the prepared hc-AC are investigated at different temperatures. The X-ray diffraction patterns indicate that pitch-based cokes prepared under high temperature and pressure have a high crystal structure. The textural properties of hc-AC indicate that it consists mainly of slit-like pores. Compared to other textural forms of AC that have higher pore volumes, this slit-poreshaped hc-AC exhibits higher CO2 adsorption due to the similar shape between its pores and CO2 molecules. Additionally, in these high-crystallinity cokes, the main factor affecting CO2 adsorption at lower temperature is the pore structure, whereas the presence of oxygen functional groups on the surface has a greater impact on CO2 adsorption at higher temperature.