Cathodic and anodic overpotentials were measured using current interruption and AC impedance spectroscopy for two separate solid oxide fuel cells (SOFCs). The fuel cells used yttria-stabilized zirconia (YSZ) as the electrolyte, strontium-doped lanthanum manganite (LSM) as the cathode, and a porous YSZ layer impregnated with copper and ceria as the anode. The Cu/CeO2/YSZ anode is active for the direct conversion of hydrocarbon fuels. Overpotentials measured using both current interruption and impedance spectroscopy for the fuel cell operating at 700ºC on both hydrogen and n-butane fuels are reported. In addition to providing the first electrode overpotential measurements for direct conversion fuel cells with Cu-based anodes the results demonstrate that there may be significant uncertainties in measurements of electrode overpotentials for systems where there is a large difference between the characteristic frequencies of the anode and cathode processes and/or complex electrode kinetics.