Although aerogels have outstanding thermal insulation performance, it is difficult to combine effectively with water-rich cementitious matrix to prepare thermal insulation coating. Herein, the composite aerogel beads (CABs) with pomegranate-like structure were synthesized to solve this problem. When CABs combined with water-rich cementitious materials, the excellent bond strength between them can reach approximately 130 KPa which was much higher than the bond strength (about 18 KPa) between water-rich cementitious materials and native aerogel. Moreover, the obtained coating presented excellent thermal insulation performance, suggesting possibilities of combining CABs and water-rich cementitious materials for thermal insulation applications of modern buildings.