Dramatic increases in fossil fuel consumption inevitably led to the emission of huge amounts of CO2 gas, causing abnormalities in the climate system. Despite continuous efforts to resolve global atmospheric problems through CO2 capture and separation, success has been limited by poor CO2 selectivity in the CO2/N2 mixture. Herein, we demonstrate the fabrication of a three-dimensional (3D) nanostructure from two-dimensional transition metal carbides (Ti3C2Tx, MXene), and assess its utility as an adsorbent in a CO2 capture system. Through structural and textural analysis, we confirm that the as-prepared MXene possesses high size uniformity with a thickness of ∼2.5 nm, and that an MXene aerogel interconnected by MXene nanosheets has a 3D porous architecture with micro/nano porosity (Barrett–Joyner–Halenda (BJH) pore size = 11.4 nm). Moreover, the MXene aerogel exhibits favorable adsorption behavior for CO2, due to the high-quality MXene nanosheets even with a low specific surface area. Our approach could lead to significant advances in CO2 capture by adsorbents and open up new opportunities for mass production.