The electrochemical behavior of new amphiphilic 1,3,4-oxadiazoles were studied by cyclic voltammetry. The influence of the supramolecular structure on the redox behavior in liquid or solid solutions, in Langmuir-Blodgett multilayers, and in amorphous films is investigated in detail. The reversible reduction of amphiphilic 2,5-diarylene-1,3,4-oxadiazoles is significantly influenced by substituents in the pala position of the phenylene ring. In the solid states the reduction peak potentials are shifted to more negative values compared to data measured in solution. This shift increases as the film thickness is increased. An influence of the supramolecular order in the solid films was not found. In-situ UV-vis spectroelectrochemistry of LB-multilayers deposited onto indium tin oxide (ITO) glass give evidence for the formation of radical anions in the highly ordered layer.