The effects of palladium doping on the catalytic activity of La0.6Sr0.4Co0.2Fe0.8O3−δ(LSCF) cathodes are investigated by comparing the performance of La0.6Sr0.4Co0.2Fe0.8−xPdxO3−δ (LSCFPd) cathodes with different doping content and LSCF cathodes. The electrochemical results show that Pd doping decreases the polarization resistance and promotes the catalytic activity of LSCF cathodes. This promotion becomes greater with the increase of Pd doping content, which is also reflected by electrical conductivity relaxation (ECR) measurement results because the oxygen surface exchange coefficient of LSCFPd is improved by Pd doping. According to the in-situ high temperature XRD and TG-DSC results, perovskite LSCFPd materials are stable at temperature below 700 °C, and some Pd species are segregated during heating process. •The effects of Pd doping on the catalytic activity of La0.6Sr0.4Co0.2Fe0.8O3−δ cathodes are investigated.•The stability of La0.6Sr0.4Co0.2Fe0.8−xPdxO3−δ perovskite materials was studied by HT-XRD and TG-DSC.•Some Pd species decompose to Pd metal at temperature above 800 °C.