In-depth probing of the surface electronic:structure on solid oxide fuel cell (SOFC) cathodes, considering the effects Of high temperature, oxygen pressure, and Material strain state, is essential toward advancing our understanding of the oxygen reduction activity on them. Here, we report the surface structure, chemical state, and electronic structure of a model transition metal perovskite oxide system, strained La0.8Sr0.2CoO3 (LSC) thin films, as a function of temperature up to 450 degrees C in oxygen partial pressure of 10(-3) mbar. Both the tensile and the compressively strained LSC film surfaces transition from a semiconducting state with an energy gap of 0.8-1.5 eV at room temperature to a metallic-like state with no energy gap at 200-300 degrees C, as identified by in situ scanning tunneling spectroscopy. The tensile strained LSC surface exhibits a more enhanced electronic density of states (DOS) near the Fermi level following this transition, indicating a more highly active surface for election transfer in oxygen reduction. The transition to the metallic like state and the relatively more enhanced DOS on the tensile strained LSC at elevated temperatures result from the formation of oxygen vacancy defects, as supported by both Our X-ray photoelectron spectroscopy measurements and density functional theory calculations The reversibility of the Semiconducting-to-metallic transitions of the electronic structure discovered here, Coupled to the strain state and temperature, underscores the necessity of in situ investigations on SOFC-cathode material surfaces.