Lithium–sulfur batteries (LSBs) have attracted tremendous interest due to their high theoretical energy density and the earth‐abundant sulfur feedstock. Multifarious characterization techniques have been applied to investigate the electrochemical mechanisms and the structure–property relationships in LSBs. Among them, cyclic voltammetry (CV), a basic electrochemical tool, can provide indispensable thermodynamic and kinetics information of the redox processes. However, the CV analysis in most LSB studies is sketchy—providing some well‐known information while ignoring some specific features. To fulfill the versatile role of CV and thus spur further breakthroughs on LSBs, the electrochemical reactions and challenges are first described, followed by the work principles and experimental setup of LSBs for the CV technique. Then, various protocols for specific research purposes in LSBs are summarized, particularly on the performance evaluation of sulfur cathodes. Ending with challenges and the outlook of the CV technique in the LSB study, the Review provides a timely summary and thus can be a guidance for future studies on batteries.