The polymer-assisted chemical solution (PACS) method was used for the synthesis of La0.8Sr0.2MnO3 (LSM)-based perovskite catalyst network with nanoparticle size of 30-80 nm to enhance oxygen evolution reaction (OER) activity and maintain highly active oxygen reduction reaction (ORR). Samples investigated include the A-site cation deficient (La0.8Sr0.2)(0.95)MnO3-delta (ALSM) and the A-site cation deficient with the B-site cobalt-doped (La0.8Sr0.2)(1-x)Mn1-xCoxO3-delta (x = 0.05 and 0.1 for LSMC5 and LSMC10, respectively). X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) aided in physical characterizations. Electrochemical properties were tested in 0.1 M KOH solution by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Our results indicate as compared to LSM, the lattice-shrunk ALSM with high oxygen vacancy displays enhanced OER performance, but its inferior ORR activity could be caused by reduced crystallinity. LSMC5 and LSMC10 show lowest total overpotential (0.93 and 0.91 V vs. Ag/AgCl (3.5 M)) with slightly less efficient ORR, despite their superior specific kinetic current density. Oxygen vacancy induces Fermi level upshift and reduced resistivity, while Co-doping increases orbital hybridization and enhances charge transfer. Understanding how the A-site non-stoichiometry and the B-site doping influence the B-O covalence is the key to the rational design of perovskite bifunctional oxygen catalysts. (c) 2018 Elsevier Ltd. All rights reserved.