The major factors limiting the electrochemical performance of a perovskite cathode for ceramic-based fuel cells are the sluggish oxygen reduction reaction (ORR) kinetics and poor durability, which are largely determined by the Asite elements. In this work, to enhance the ORR activity and stability, we present an effective strategy of tuning the A-site dopant in a layered double perovskite oxide of Ba 0.8 Gd 0.8 Pr 0.4 -Co 2 O 6−δ (BGPC). When applied as a cathode on a La 0.8 Sr 0.2 -Ga 0.8 Mg 0.2 O 3−δ (LSGM) electrolyte-supported cell, it demonstrates high electrochemical performance, achieving an areaspecific resistance (ASR) of 0.170 Ω cm 2 , and a peak power density (PPD) of 1.189 W cm −2 at 800°C, better than those acquired from a state-of-the-art (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3−δ (LS95CF)-based cathode. The single cells with the BGPC cathode exhibit better performance and stability (a degradation rate of 0.074% h −1 ) than the cells with the LS95CF cathode (a PPD of 1.079 W cm −2 at 800°C and a degradation rate of 0.13% h −1 ) under the same operating conditions. By the electrochemical performance evaluation and characterizations, it is suggested that A-site tuning on a double-perovskite oxide can be a promising strategy to enhance the electrode activity and durability of fuel cells.