A series of sulfonate-based silicone surfactants with different hydrophobic groups were synthesized. Two synthetic strategies are introduced to permit exquisite control over the hydrophobic moieties. Solution behavior of these surfactants was investigated by surface tensiometry, electrical conductivity, transmission electron microscopy, and dynamic light scattering. The results indicate that the aqueous behavior of the surfactants was distinctly influenced by the hydrophobic groups. Subtle distinctions in surfactant-related properties, which can be attributed to the three-dimensional molecular structures of the surfactants, can be seen for compounds with different hydrophobic moieties. Contact angle results of these surfactants indicate that they have super dispersal ability with the potential value in agriculture.