The salinity seriously affects the recovery efficiency of surfactant flooding, and it is demonstrated the introduced ethoxy (EO) groups can enhance the interfacial activity of surfactants at harsh salinity via various experimental methods. In this study, sodium dodecyl sulfate (SDS) and sodium dodecyl ether sulfate (AES) are selected to investigate the effects of EO group number on the salt resistance of surfactants at the air/water interface by experiments and molecular dynamics (MD) simulation method. Optical microscopy and static multiple light scattering results show that the AES stabilized emulsions with Ca2+ ions have better stability than those of SDS, which is further explored by molecular MD simulation method. The interface formation energy (IFE) and self-diffusion coefficients (Dα) are calculated to systematically study the effects of introduced EO group number on calcium resistance of surfactants. The interaction between surfactants and Ca2+ ions at the oil/water interface is evaluated by the potential of mean of force (PMF) and the radial direction functions (RDF), which is confirmed by the calculation of molecular electrostatic potential (MEP) and coordination number. The simulation results indicate that the introduced EO groups can combine Ca2+ ions to fabricate salt bridge via intermolecular or intramolecular interactions to highly improve the calcium resistance of surfactants. The present work proposes a microcosmic perspective of the roles of EO group number on the calcium resistance of AES at the oil/water interface.