Specific ion effects at aqueous interfaces play key roles in many important phenomena. We recently reported that ions interact specifically over unexpectedly long distances on the surface of sub-micromolar electrolyte solutions (Enami et al. J. Chem. Phys. 2012, 136, 154707). Whether the anionic and cationic headgroups of the organic amphiphiles present at most water/hydrophobe interfaces act similarly or display new behaviors, however, is not known. Here we report the results of experiments in which we apply online electrospray ionization mass spectrometry (ESI-MS) to investigate how carboxylate, RCOO- (R = CH3, C5H11, C7H15), and alkylammonium, R'(CH3)(3)N+ (R' = CH3, C14H29), ions affect the ratio chi = I-/Br- at the aerial interface of 1 mu M (NaI + NaBr) aqueous solutions. We found that chi is systematically but selectively depressed by these ionic amphiphiles and minimally affected by the neutral surfactant 1-octanol. The depressing effects induced by cationic headgroups are stronger than those caused by anionic surfactants and always increase with the length of the alkyl chains.