Silicone surfactants consist of siloxane or carbosilane hydrophobic groups that possess better surface activity compared with alkane surfactants. The surfactants, containing Si atoms which bring excellent bond flexibility and low cohesive energy properties are a promising class of materials for unique surface working, but there are few studies to elaborate their surface activity mechanism with regard to the molecular architecture. Herein, two novel carboxylate surfactants with different silicone hydrophobic groups (Si-O-Si and Si-C-Si) were synthesized and their surface activities, aggregate behaviors, and solution stabilities were systematically investigated. Results showed that both surfactants had excellent surface activities which are attributed to the hydrophobic structure of silicone. The hydrolysis resistance of the carbosilane-based carboxylate surfactant was better than that of the siloxane-based carboxylate surfactant. The differences in hydrolysis processes for the surfactants were confirmed by the mass spectrum and kinetic analysis. Meanwhile, the aggregation number of Si-C-Si surfactants was also determined by the fluorescence quenching method for the first time.