Abstract: Rechargeable lithium–sulfur batteries have aroused great attention in recent years. Thousands of research articles are published, and among these publications, the majority are dedicated to improving the battery's performance through chemically and physically modifying the sulfur electrode, electrolytes, separator, and lithium anode. However, the single most important aspect, understanding the sulfur redox mechanism, is sparse and overwhelmed by the huge volume of work done on improving the battery's performance. Besides the intrinsic complexity of the sulfur redox chemistry, the most challenging task is to find an effective analytical technique for the quantitative and qualitative determination of the dissolved and solid polysulfides, including elemental sulfur. In this paper, the recent important research aiming to understand the redox mechanism of the sulfur electrode is reviewed in light of the unique analytical techniques used in the research. The review re‐affirms the complexity of the sulfur redox chemistry and lays the background for the future mechanistic research for Li–S batteries. [ABSTRACT FROM AUTHOR]