The current scientific community is extensively involved in developing novel materials for energy and environmental applications. Capture of CO₂ to remove it from the atmosphere is one of the most important applications among them. In the present work, we have demonstrated for the first time, to the best of our knowledge, a polyaniline–graphene nanocomposite as a CO₂ capture candidate. Graphene was prepared by hydrogen induced thermal exfoliation of graphite oxide and was further coated with polyaniline using a chemical method. The nanocomposite was characterized by different techniques and the capture capacity was measured using a high pressure Sievert’s apparatus. FTIR spectroscopy was used to confirm the possible CO₂ capture mechanism in the nanocomposite. CO₂ adsorption capacities at a pressure of 11 bar and different temperatures of 25, 50 and 100 °C were experimentally found to be 75, 47 and 31 mmol g⁻¹, respectively. This nanocomposite shows much higher CO₂ capture capacity compared to pure graphene and shows a high degree of recyclability.