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.