Solid supported lipid films have proved very useful both as biomembrane mimetic analogs and as a basis for electrode modifications in the construction of sensor devices. The films are prepared in quite different manner, including liposome spreading, self-assembly, Langmuir-Blodgett (LB), or cast film technique. An alternative method of formation is achieved through the thinning of wetting lipid films on solid surfaces, submersed in electrolyte solution. The impact of some divalent cations on the structure of a model membrane system has been investigated with several types of supported lipid film, comprising wetting lipid films. Changes in the films capacitance and resistance and opening of channel-like defects in supported lipid films have been reported. This work represents further investigations of the effects caused by the divalent cations on the formation and structure of wetting lipid films. The impedimetric and voltammetric results suggest significant influence of Mn2+, Mg2+, Ca2+ on the packing order and strengthening of the lipid structure of the film.