Anion redox in lithium transition-metal oxides such as Li2RuO3 and Li2MnO3 has catalyzed intensive research efforts to find transition-metal oxides with anion redox that may boost the energy density of lithium-ion batteries. The physical origin of the observed anion redox remains debatable, and more direct experimental evidence is needed. In this work, we have shown electronic signatures of oxygen–oxygen coupling, direct evidence central to lattice oxygen redox (O2–/(O2) n−), in charged Li2–x RuO3 after Ru oxidation (Ru4+/Ru5+) upon first electron removal with lithium deintercalation. Experimental Ru L3-edge high-energy-resolution fluorescence-detected X-ray absorption spectra (HERFD-XAS), supported by ab initio simulations, revealed that the increased intensity in the high-energy shoulder upon lithium deintercalation resulted from increased O–O coupling, inducing (O–O) σ*-like states with π overlap with Ru d-manifolds, in agreement with O K-edge XAS spectra. Experimental and simulated O K-edge X-ray emission spectra further supported this observation with the broadening of the oxygen nonbonding feature upon charging, also originated from (O–O) σ* states. This lattice oxygen redox of Li2–x RuO3 was accompanied by a small amount of O2 evolution in the first charge from differential electrochemistry mass spectrometry but diminished in the subsequent cycles, in agreement with the more reduced states of Ru in later cycles from Ru L3-edge HERFD-XAS. These observations indicated that Ru redox contributed more to discharge capacities after the first cycle. This study has pinpointed the key spectral fingerprints related to lattice oxygen redox from a molecular level and constructed a transferrable framework to rationally interpret the spectroscopic features by combining advanced experiments and theoretical calculations to design materials for Li-ion batteries and electrocatalysis applications.