Electrochemical scanning tunneling microscopy (EC-STM) has been employed to study the structure of a film formed by cationic surfactant N-decyl-N,N,N-trimethylammonium triflate (DeTATf) adsorbed on the Au(111) electrode surface. The film is disordered at potentials corresponding to either large negative,charge densities or to positive charge densities. At small negative charge densities, an ordered adlayer of flat-lying DeTATf molecules is formed. High-resolution images of this adlayer reveal that the triflate anion is coadsorbed with the N-decyl-N,N,N-trimethylammonium cation, effectively forming an ion pair at the electrode surface. This is a significant result because it explains why this surfactant behaves like a zwitterionic surfactant at the metal/solution interface.