An electrochemical cell [Au/yttria-stabilized zirconia (YSZ)/Au] serves as a model system to investigate the effect of O2 and NOx. Possible mechanisms responsible for the response are presented. Two dense Au electrodes are co-located on the same side of a dense YSZ electrolyte and are separated from the electrolyte by a porous YSZ layer, present only under the electrodes. While not completely understood, the porous layer appears to result in enhanced NOx response. Impedance data were obtained over a range of frequencies 0.1 Hz to 1 MHz, temperatures 600–700°C, and oxygen 2–18.9% and NOx 10–100 ppm concentrations. Spectra were fit with an equivalent circuit, and values of the circuit elements were evaluated. In the absence of NOx, the effect of O2 on the low-frequency arc resistance could be described by a power law, and the temperature dependence by a single apparent activation energy at all O2 concentrations. When both O2 and NOx were present, however, the power-law exponent varied as a function of both temperature and concentration, and the apparent activation energy also showed dual dependence. Adsorption mechanisms are discussed as possibilities for the rate-limiting steps. Implications for impedancemetric NOx sensing are also discussed.