It is evident that the exhaustive use of fossil fuels for decades has significantly contributed to global warming and environmental pollution. To mitigate the harm on the environment, lithium-oxygen batteries (LOBs) with a high theoretical energy density (3458 Wh kg-1Li2O2) compared to that of Li-ion batteries (LIBs) have been considered as an attractive alternative to fossil fuels. For this purpose, porous carbon materials have been utilized as promising air cathodes owing to their low cost, lightness, easy fabrication process, and high performance. However, the challenge thus far lies in the uncontrollable formation of Li2CO3 at the interface between carbon and Li2O2, which is detrimental to the stable electrochemical performance of carbon-based cathodes in LOBs. In this work, we successfully protected the surface of the free-standing carbon nanofibers (CNFs) by coating it with a layer of iridium metal through direct sputtering (CNFs@Ir), which significantly improved the lifespan of LOBs. Moreover, the Ir would play a secondary role as an electrochemical catalyst. This all-in-one cathode was evaluated for the formation and decomposition of Li2O2 during (dis)charging processes. Compared with bare CNFs, the CNFs@Ir cathode showed two times longer lifespan with 0.2 VLi lower overpotentials for the oxygen evolution reaction. We quantitatively calculated the contents of CO32- in Li2CO3 formed on the different surfaces of the bare CNFs (63% reduced) and the protected CNFs@Ir (78% reduced) cathodes after charging. The protective effects and the reaction mechanism were elucidated by ex situ analyses, including scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy.