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We report the first study that investigates the use of molten carbonates as an effective catalyst to promote electrochemical oxygen reduction reaction (ORR) at the cathode of intermediate temperature solid oxide fuel cells (IT-SOFCs). A series of binary Li-K carbonate compositions were incorporated into the porous backbones of a commercial cathode assembled in symmetrical impedance cells for electrochemical characterization. Within the temperature range of 550–650◦C, we observed that the polarization and ohmic area-specific resistances of the original sample can be significantly reduced by the introduction of molten carbonates. A new ORR charge-transfer model involving two intermediate species CO5 2− and CO4 2− as the fast oxygen absorber and transporter, respectively, was presented as the mechanism for the facile ORR kinetics promoted by molten carbonates.