A symmetric PBCO/YSZ/PBCO cell (where PBCO refers to PrBaCo₂O_5.5+δ, and YSZ to yttria stabilized zirconia) was designed and fabricated for the investigation of the catalytic nature and reaction kinetics of CO₂ on PBCO surfaces. The electrochemical impedance spectroscopy was employed to probe the CO₂ reaction behavior on the PBCO electrode. The symmetric equivalent circuit cell characterization reveals that the surface resistance of CO₂ on PBCO is only 30.2 Ω cm² and the maximum surface exchange coefficient k_chem is 2.0 × 10⁻⁴ cm s⁻¹ at 1147 K, suggesting that PBCO can be an excellent candidate for CO₂ reduction.