The features of interfacial water at air-water interfaces of anionic sodium dodecyl sulfate (SDS) and cationic dodecyl amine hydrochloride (DDA) solutions were examined by combining sum frequency generation (SFG) vibrational spectroscopy measurements and molecular dynamics simulations (MDS). The SFG spectra revealed that interfacial water molecules for SDS solutions were highly ordered compared with those for DDA solutions. To elucidate this observation, in addition to agreement with the literature in regards to the interfacial electric field at the interfaces, we investigated the features of interfacial water molecules with respect to their network and their interaction with surfactant head groups. Our simulation analysis results revealed a higher number density, more strongly connected hydrogen bonding, and more orderly oriented interfacial water molecules at the interface of the SDS solutions as compared to the DDA solutions. The goal of this research is to identify significant features of interfacial water for our improved understanding of such interfacial phenomena.