<p>This study evaluates the effect of synthesis mode and La-dopant incorporation on the performance of CeO₂-based materials for CO₂ capture. Materials were prepared by conventional autoclave and microwave-assisted hydrothermal treatments to compare their efficacy. Microwave-assisted synthesis enables rapid and uniform volumetric heating, accelerating nucleation and crystal growth, consequently shortening synthesis time. Samples were characterized by powder X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy– Energy-Dispersive X-ray Spectroscopy (SEM-EDS), Brunauer–Emmett–Teller (BET) analysis for surface area and pore volume, alongside CO₂ adsorption measurements at 273&#xa0;K. Microwave irradiation yielded CeO₂ with smaller crystallites and higher surface area (107 m²⋅g^− 1) compared to the conventional hydrothermal method. The corresponding CO₂ uptake for the microwave-assisted materials was 1.21 mmol⋅g^− 1. Furthermore, La-doped samples exhibited stronger basic sites and altered Ce⁴⁺/Ce³⁺ ratios, favouring the formation of bidentate and polydentate carbonates. CO₂ adsorption data correlated better with the Freundlich model, and the adsorption kinetics were best described by the pseudo-second-order model. The results demonstrate that microwave-assisted hydrothermal synthesis effectively tailored the surface properties of CeO₂-based materials, enhancing both interaction strength with CO₂ and overall CO₂ adsorption capacity.</p>