In this work, novel and cheap CO2 imprinted adsorbents were synthesized on the surface of activated carbon derived from sunflower heads by surface imprinting technique using ethanedioic acid and acrylamide as template molecule and functional monomer, respectively. To obtain CO2 imprinted adsorbents with optimal properties, we studied the effects of ratio of KOH to sunflower-based activated carbon, carbon dosage and adsorption temperature, and found that the optimal conditions were alkali carbon ratio of 0.75:1, carbon dosage of 0.75 g, and adsorption temperature of 20°C. Under these conditions, maximum CO2 adsorption capacity of the adsorbents can attain 1.71 mmol g–1. The selective adsorption performance of the adsorbents for CO2 was studied in the presence of H2O as well as in simulated flue gas. In addition, the adsorbents after adsorption can be effectively regenerated by N2 purge at 120°C. After five adsorption/desorption experiments, the CO2 adsorption capacity only decreased 11%. The results showed that sustainable and cheap CO2 imprinted adsorbents have good adsorption, selectivity and regeneration properties, which are worth being further studied and applied in CO2 capture.