The surface adsorption of the O, O′-bis(sodium 2-lauricate)- p-benzenediol (C11 pPHCNa) and dodecyltrimethylammonium bromide (C 12TABr) aqueous mixtures was examined by surface tension method. Strong synergism between the two components was observed, which leaded to high effectiveness and efficiency in surface tension reduction. The maximum effectiveness and efficiency in surface tension reduction appeared at the mole fraction of C11 pPHCNa in the bulk ( α 1) being 0.33, where the two components equal electrical mixing in solution. The corresponding minimum surface tension ( γ cmc) and the total concentration required to reduce 20 mN m −1 surface tension of water ( C 20,T) were, respectively 25.2 mN m −1 and 2.02 × 10 −3 mmol L −1. The maximum apparent surface excess, Γ max was observed at α 1 = 0.1 rather than at α 1 = 0.33. The cause was attributed to two aspects: (1) the considerable fast diffusion rate of C 12TABr in comparison with C11 pPHCNa and (2) significantly high hydrophobicity of the latter. The unusually small apparent area of the adsorbed molecule suggested the surface aggregates formation. The pattern of the surface aggregates was further described as the double layers structure in the subsurface by analyzing the data of the total area of all adsorbed molecules.