A new aprotic solvent system for POD is described allowing to develop new possibilities for processing these polymers. In comparison to concentrated sulfuric acid where the beta-form is formed in the precipitation process the aprotic solvent system gives the possibility to make the POD-alpha-structure directly. The beta-form is characterized by a predominantly two-dimensional order whereas the alpha-structure is distinguished by a relatively high degree of three-dimensional order. The determination of both POD-supra molecular structure by IR- spectroscopy is also described. Additional, the electrochemical doping processes of poly (p-phenylene-1, 3, 4-oxadiazole) (p-POD) and the corresponding m-isomer are investigated. p-POD can easily be n-doped electrochemically and the resulting electronic structure supports a facile charge transport. In contrast m-POD was electrochemically inactive. The relationship between the molecular structures as well as the supra molecular structures and the electrochemicalical behavior is shortly discussed. electronic structure supports resulting charge