This study uses electrochemical impedance spectroscopy (EIS) to characterize an LSM/CGO symmetric cell modified by NOx adsorbents for the application of electrochemical NOx reduction. Three cells were prepared and tested: a blank cell, a cell impregnated with BaO, and a cell coated with a BaO-Pt-Al2O3 layer. The impedance analysis revealed that modification with the NOx adsorbents, either by impregnating the BaO into the electrode or by adding a BaO-Pt-Al2O3 layer on top of the electrode significantly enhanced the electrode activity. This activity enhancement was mainly due to the decrease in the resistance of the low-frequency processes, which were ascribed to adsorption, diffusion, and transfer of O2 species and NOx species at or near the triple phase boundary (TPB) region and the formation of the reaction intermediate NO2. The BaO impregnation improved the adsorption of NOx on the LSM/CGO electrode by selectively trapping NO2 in the form of nitrate over the BaO sites and provided availability for a direct reduction of the stored nitrate. The BaO-Pt-Al2O3 layer enhanced the NOx adsorption and promoted the formation of NO2 due to the NO oxidation ability of the Pt catalyst, but hindered the gas diffusion to the reaction sites.