Calcium oxide (CaO) is a promising adsorbent to separate CO₂ from flue gas. However, with cycling of carbonation/decarbonation at high temperature, the serious sintering problem causes its capture capacity to decrease dramatically. A CaTiO₃-decorated CaO-based CO₂ adsorbent was prepared by a continuous and simple aerosol-assisted self-assembly process in this work. Results indicated that CaTiO₃ and CaO formed in the adsorbent, whereas CaO gradually showed a good crystalline structure with increased calcium loading. Owing to the high thermal stability of CaTiO₃, it played a role in suppressing the sintering effect and maintaining repeated high-temperature carbonation and decarbonation processes. When the calcium and titanium ratio was 3, the CO₂ capture capacity was as large as 7 mmol/g with fast kinetics. After 20 cycles under mild regeneration conditions (700 °C, N₂), the performance of CO₂ capture of CaTiO₃-decorated CaO-based adsorbent nearly unchanged. Even after 10 cycles under severe regeneration conditions (920 °C, CO₂), the performance of CO₂ capture still remained nearly 70% compared to the first cycle. The addition of CaTiO₃ induced good and firm CaO dispersion on its surface. Excellent kinetics and stability were evident.