Density functional theory (DFT) of quantum chemistry was used to optimize the configuration of the anionic surfactant complexes CH3(CH2)7OSO-3(H2O)n (n=0-6) and calculate their molecular frequencies at the B3LYP/6-311+G* level. The interaction of CH3(CH2)7OSO-3 with 1 to 6 water molecules was investigated at the air-water interface with DFT. The results revealed that the hydration shell was formed in the form of H-bond between the hydrophilic group of CH3(CH2)7OSO-3 and 6 waters. The strength of H-bonds belongs to medium. Binding free energy revealed that the hydration shell was stable. The increase of the number of water molecules will cause increases of the total charge of hydrophilic group and S10-O9-C8 bond angle, but decreases of the alkyl chain length and the bond lengths of S10-O11,S10-O12 as well as S10-O13, respectively.