Owing to unique catalytic properties and durability, nanoparticles-containing heterostructured catalysts have attracted much interest in energy storage and conversion fields. Here we report a multi-composite electrocatalyst consisting of BaO nanoparticles and Ln0.94BaCo2O5+δ (Ln = La, Pr, Nd, Sm, and Gd) (e-Ln0.94BCO) though in situ exsolution route. As-obtained e-Ln0.94BCO catalysts exhibit desirable oxygen reduction reaction (ORR) activity and durability toward solid oxide fuel cells (SOFCs) cathode application. When varying Ln3+ from Gd3+ to La3+, the phase transformation of orthorhombic-tetragonal-cubic can be identified in Ln0.94BaCo2O5+δ, significantly demonstrating improved electrochemical performance as well as electrical conductivity, oxygen surface exchange and chemical diffusion coefficients. Resultantly, the e-L0.94BCO cathode exhibits the lowest area-specific resistance (ASR) of 0.03 Ω cm2 at 700 °C, reduced by ≈ 43% relative to pristine La0.94BaCo2O5+δ (L0.94BCO) cathode. Under realistic operating conditions, the e-L0.94BCO cathode-based button cell delivers a peak power density (PPD) 0f 1.05 W cm−2 at 700 °C, along with outstanding long-term stability. Furthermore, an exceptional CO2 durability is achieved in e-L0.94BCO with negligible degradation rate. Density-functional theory (DFT) calculations imply that interfacial BaO makes a movement of O 2p-band center to the Fermi level, which is closely related to promoted electrochemical performance.