As the lightest and cheapest transition metal dichalcogenide, TiS2 possesses great potential as an electrode material for lithium batteries due to the advantages of high energy density storage capability, fast ion diffusion rate, and low volume expansion. Despite the extensive investigation of its electrochemical properties, the fundamental discharge–charge reaction mechanism of the TiS2 electrode is still elusive. Here, by a combination of ex situ and operando X-ray absorption spectroscopy with density functional theory calculations, we have clearly elucidated the evolution of the structural and chemical properties of TiS2 during the discharge–charge processes. The lithium intercalation reaction is highly reversible and both Ti and sulfur are involved in the redox reaction during the discharge and charge processes. In contrast, the conversion reaction of TiS2 is partially reversible in the first cycle. However, Ti—O related compounds are developed during electrochemical cycling over extended cycles, which results in the decrease of the conversion reaction reversibility and the rapid capacity fading. In addition, the solid electrolyte interphase formed on the electrode surface is found to be highly dynamic in the initial cycles and then gradually becomes more stable upon further cycling. Such understanding is important for the future design and optimization of TiS2 based electrodes for lithium batteries.