The dependence of the impedance of low-temperature sensors for carbon dioxide based on the solid-state electrochemical cells Na0.5WO3/Na5GdSi4O12/SnO2(Sb2O4) on the concentration of carbon dioxide in the air was studied. The reversible change in the sensor resistance was shown to be due to adsorption processes at intergrain boundaries of the solid electrolyte. The composition of the products of the electrochemical processes occurring in the sensors was established.