Redox-active polyelectrolyte-surfactant complexes (PSC) were prepared via the ionic self-assembly of sodium poly(styrenesulfonate) (PSS) and ferrocenyl surfactant,(11-ferrocenylundecyl)trimethylammonium bromide (FTMA) in aqueous solution.The PSS-FTMA complex exhibited an ordered interdigitated monolayer mesomorphous structure with the long period of d =3.13 nm,and was in the ionic thermotropic liquid crystal SmA state at room temperature.Interestingly,in the solid complex,the ferrocenyl moieties formed H-aggregation showing an increase in the π-π* energy transfer of cyclopentadienes in the ferrocene moieties as known from the blue-shift in the UV spectrum.The complexes showed higher thermal stability compared with their components due to the ionic interaction.The PSS-FTMA film had a good redox reversibility,which promised to be used in electrochemical sensors.