The anode/electrolyte interface ш solid oxide fuel cells (SOFC) is known to cause electrical losses. Geometrically simple Ni yttria-stabilised zirconia (YSZ) interfaces were examined to gain information on the structural and chemical changes occurring during experiments at 1000°C in an atmosphere of 97% H2/3% H20. Electrochemical impedance spectroscopy at open circuit voltage (OCV) and at anodic and cathodic polarisations (100 mV) was performed. A correlation of the electrical data with the structure development and the chemical composition was attempted. Nickel wires with different impurity content (99.8% Ni and 99.995% Ni) were used to examine the impact of impurities on the polarisation resistance and contact area morphology. The electropolished nickel wires were pressed against a polished 8 mol% YSZ surface.Extensive structural changes from a flat interface to a lull and valley structure were found to occur ш the contact area with the impure nickel wire, and a ridge of impurities was built along the rim of the contact area. Impurity particles in the interfacial region were also observed. The impurity phase was described as an alkali silicate glassy phase. No differences were found between polarised and non-polarised samples. With pure nickel wires, however, the microstructures depended on the polarisation /non-polarisation conditions. At non-polarised conditions a hill and valley type structure was found. Anodic polarisation produced an up to 1 um thick interface layer consisting of nano-sized YSZ particles with some Ni present. At cathodic polarisation both a granulated structure and a lull and valley structure resembling the structure of non-polarised samples were found. Small impurity ridges were surrounding the contact areas on non-polarised and cathodically polarised samples. TOF-SIMS and XPS analyses showed the presence of impurities in both the impure and pure contact areas. The impedance spectroscopy revealed that depending on the impurity content of the nickel, different developments of the polarisation resistance with time took place. At open circuit voltage the samples with impure nickel electrodes showed an initial increase toward a high constant polarisation resistance, whereas the samples with pure nickel electrodes showed a considerable decrease to a low constant polarisation resistance with time. For both types of nickel the polarisation resistance dropped upon polarisation. The area specific polarisation resistances for the samples with pure electrodes were approximately 10 times lower than for samples with impure electrodes. This was mainly ascribed to the impurity content and distribution, both in the three phase boundary zone and as a more or less continuous film covering the interfacial region. The drop in the Rp upon polarisation may be ascribed to changes ш the distribution of the impurity phase in the interfacial region.