Studies at the Otto-von-Guericke-University of Magdeburg in cooperation with oelheld GmbH in Stuttgart have analyzed the influence of selected additives in dielectric working fluids for electrical discharge machining (EDM) on the ignition and breakdown phases of the plasma channel. The electrical breakdown in the hydrocarbon base fluid without additives is determined by the formation of the external Helmholtz-Layer as an interface between electrode surface and dielectric medium. The influence of the different additive molecules on the formation of the HelmholtzLayer and on the ignition and discharge mechanism will be discussed.