The article examines membrane permeability and reassembled behavior due to the surfactant hexadecyl trimethyl ammonium bromide (HTABr) addition. The influence of HTABr on s-BLMs was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The experimental results show that the HTABr appeared to be an effective ion carrier to facilitate the transmembrane transportation of ferrocyanide/ferricyanide. The permeability of s-BLMs changes with time and concentration of surfactant addition. At the same time, it is interesting to note that phosphatidylcholine molecules can self-assemble again on the surface of Pt electrode within limitative time and/or concentration of surfactant addition. The phenomenon of transmembrane transportation of ferrocyanide/ferricyanide disappeared in the absence of the surfactant hexadecyl trimethyl ammonium bromide.