<p>Electrolyte plays a pivotal role in enhancing the overall performance of lithium (Li) batteries, as they not only serve as the medium for Li ions transport but also mainly determine the stability of the electrode/electrolyte interfaces. Siloxane molecules possess several advantages, including high (electro)chemical stability, wide liquid temperature range, and high thermal stability. Hence, siloxane-based electrolytes have emerged as novel electrolyte systems and received intensive attention to overcome the shortcomings of the state-of-the-art electrolytes. In this review, a comprehensive overview of recent advances in siloxane-based liquid electrolytes is summarized. First, the intrinsic properties of siloxane-based electrolytes and their superior tolerance to high voltage and high/low temperatures are discussed. Subsequently, the latest research progress of siloxanes as solvents or additives are reviewed in Li batteries with Li metal, graphite, and Si anodes, respectively. Finally, future research directions are proposed to provide theoretical guidance for the design of high-performance siloxane-based electrolytes.</p>