Langmuir-Blodgett lipid films deposited onto glassy carbon electrodes were analyzed by comparing the voltammetric profiles of the Ru(NH3)(6)(3+) /Ru(NH3)(6)(2+) and Fe(CN)(6)(3-)/Fe(CN)(6)(4-) redox couples. The responses were correlated with the behavior of the lipid monolayers at the air \ water interface giving the same tendency in the compressibility factors as in the electrochemical blocking effect. Digital simulation of some current-potential profiles was successfully done in the case of the Ru(NH3)(6)(3+)/Ru(NH3)(6)(2+) couple, which proved to be a better marker ion as it does not have the well known drawbacks of the Fe(CN)(6)(3-)/Fe(CN)(6)(4-) couple. A model which considers the effect of macroscopic inhomogeneities of the surface on the electrochemical response was used.