The interfacial assembly process and configuration of the pseudogemini surfactant fabricated by sodium dodecyl benzene sulfonate (SDBS) and 4,4'-oxydianilinium chloride (ODC) were studied using quantum mechanical calculations and molecular dynamics (MD) simulations. The MD simulation results revealed that SDBS and ODC showed the vertical and horizontal arrangements at the oil/water interface, respectively, and the interfacial assembled configuration presented an unexpected "H" shape rather than the traditional "U" shape. The radial distribution functions between the head groups and water molecules were employed to explore the effects of the surrounding water molecules on the SDBS/ODC interaction. Furthermore, the results of the nonbonded interaction calculations and the reduced density gradient method directly confirmed that the cation-π interaction should be responsible for the SDBS/ODC assembly mechanism and the final configuration at the oil/water interface.