Transition metal (Me = Cu, Fe, Ni) doped (Pr, Ba)Co2O5+δ (PBCO) material were investigated in terms of electronic structure change and electrochemical properties. It was confirmed that (Pr, Ba)(Co, Cu)O5+δ (PBCCu) and (Pr, Ba)(Co, Fe)O5+δ (PBCFe) showed cubic and orthorhombic structures, respectively, but (Pr, Ba)(Co, Ni)O5+δ (PBCNi) showed secondary phases. PBCCu has an average particle diameter of 1093 nm, and PBCO and PBCFe have an average particle diameter of 495.1 nm and 728 nm, respectively. The average oxidation values of B site ions in PBCMe were calculated to be 3.26 (PBCO), 2.48 (PBCCu), 3.32 (PBCFe), and valence band maximum (VBM) was -0.42 eV (PBCO), -0.58 eV (PBCCu), 0.11 eV (PBCFe). It is expected that PBCCu easily interacts with adsorbed oxygen due to the lowest oxidation value and the highest VBM. The polarization esistance was 0.91 Ωcm2 (PBCO), 0.77 Ωcm2 (PBCCu), 1.06 Ωcm2 (PBCFe) at 600°C, showing the lowest polarization resistance of PBCCu.