At present, the Li₄SiO₄ sorbents have been getting widespread attention for mitigating the release of CO₂ gas owing to its stable cyclic property, higher capturing ability, and lower regeneration temperatures. In this work, a facile rolling ball method is first proposed to fabricate Li₄SiO₄ sorbent pebbles, which overcomes the low production efficiency, poor adsorption stability, and high production cost adopted in the previous literature. In the rolling ball process, the spray granulation process was involved to decrease the specific surface area of ceramic powder, which makes it easier for powder self-agglomerate to form pebbles via the centrifugal force with the assistance of PVA polymer solution. Moreover, the phase composition, the specific surface area, the shaping principle, and the microstructure of Li₄SiO₄ sorbent pebbles were studied, respectively. The result shows that the Li₄SiO₄ pebbles sintered at 900 °C for 2 h present a superior comprehensive performance with a homogeneous diameter of 1.2 mm, good sphericity of 0.95, high crushing load of 65 N, and suitable porosity of 6.28 %. Compared with Li₄SiO₄ powder, the spherical pebbles performed superior CO₂ adsorption ability (0.304 g CO₂/g sorbent) and excellent cyclic stability in a 100% CO₂ environment owing to its large number of uniform pores channels produced by binder solution at high temperature. Therefore, the rolling ball process is a potential method for the batch production of Li₄SiO₄ pebbles to capture CO₂ stably in the future.