The field of biomimetic planar lipid membranes is finding increased importance as the need to devise sensing systems for biologically important species increases. We approach this area with an eye toward understanding how to interrogate local organization in these complex media. Our primary tools for this purpose are spectroscopy and electrochemistry, where imbedded reporter molecules serve as the information transducers. We use Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) methods to construct planar lipid membranes on hydrophilic solid substrates (Au for electrochemistry, SiO x for spectroscopy). Pyrene tethered to the substrate acts as our probe and AC voltammetry was used to evaluate its redox kinetics, showing slow, distance independent electron transfer between the pyrene moieties and the electrode for both monolayer and bilayer systems. Time-resolved fluorescence data indicate that tethered pyrene resides in a highly rigid environment and that the addition of the top lipid leaflet improves the organization of the bottom lipid leaflet. These data point to the cooperative effect of the bilayer leaflets in creating a system that is comparatively rigid on short length scales, and capable of mediating motion and accessibility of imbedded species.