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The present work reports a systematic study on temperature-dependent local crystal structure, oxygen stoichiometry, and electrical/electrochemical properties of an oxygen-deficient Sr_0.9Y_0.1CoO_3−δ (SYC10) perovskite using variable-temperature neutron diffraction (VTND), thermal gravimetric analysis, and electrical/electrochemical methods, respectively. The VTND reveals that the crystal symmetry of SYC10 remains P4/mmm tetragonal up to 900 °C. The tetragonal symmetry reflects the net effects of temperature and oxygen stoichiometry on crystal symmetry. The observed p-type electronic conductivity behavior originates from the charge-ordering between the two distinctive Co-sites. The partial oxide-ion conductivity and diffusivity obtained from oxygen permeation measurements are 2.3 × 10^–2 S cm^–1 and 7.98 × 10^–8 cm²/s at 800 °C in air, respectively. The electrochemical oxygen reduction reaction kinetics …