The present-day high-temperature solid oxide fuel cells (SOFCs), based on yttria-stabilized zirconia (YSZ) electrolyte, a lanthanum-strontium manganite (LSM) cathode and a nickel-YSZ cermet anode, operate at . Cathode materials are restricted to doped lanthanum manganites due to their stability in oxidizing atmosphere, sufficient electrical conductivity, and thermal expansion match to the YSZ electrolyte. Reduction in the operating temperature of SOFCs is desirable to lower the costs and to overcome the technological disadvantages associated with elevated temperatures. However, as the operating temperature is reduced, the decrease in the LSM conductivity and increase in interfacial polarization resistances between the LSM cathode and YSZ electrolyte become critical. Therefore, different approaches have been proposed to improve interfacial quality and electrochemical performance of the LSM/YSZ cathode. The length of the triple-phase boundary (TPB) correlates well with the interfacial resistances to electrochemical oxidation of hydrogen at the anode and reduction in oxygen at the cathode. The extension of the TPB or the number of active reaction sites becomes, therefore, a determining factor in improving electrode performance. This can be achieved by developing electrode materials of higher ambipolar conductivity and by optimizing the microstructure of the electrodes. In order to improve SOFC performance, both composition and structure of the LSM/YSZ interface and of the cathode should be optimized. Recently, functional grade materials (FGMs) were introduced for SOFC technology. However, all studies reported in the literature so far, were focused on cathodes with only compositional gradient. On the other hand, intuitionally the best structure for a functional SOFC should be characterized by both compositional and porosity gradients. Fine grains (and high surface area) close to the electrode/electrolyte surface and large grains (and thus large pore size) at the air/oxygen side are expected to be of advantage. In the present study, “symmetrical” cathode-electrolyte-cathode SOFC single cells were fabricated. The cells consisted of the functional grade LSM cathode with YSZ/LSM cathode functional layer and LSM contact layer. The effects of various geometrical and microstructural parameters of cathode/functional layers on the overall cell performance were systematically investigated. The parameters investigated were the (1) cathode functional layer thickness and grain size and (2) the LSM contact layer thickness. Cathode performances were tested by means of electrochemical impedance spectroscopy (EIS) over a temperature range of , using air as oxidant. The dependence of cell performance on various parameters was rationalized by a comprehensive microscale model. A cathode polarization corresponding to at was achieved in this manner.