Realizing solid‐state lithium batteries with higher energy density and enhanced safety compared to the conventional liquid lithium‐ion batteries is one of the primary research and development goals set for next‐generation batteries in this decade. In this regard, polymer electrolytes have been widely researched as solid electrolytes due to their excellent processability, flexibility, and low weight. With high cationic transference numbers (tLi+ close to 1), single‐ion conducting polymer electrolytes (SICPEs) have tremendous advantages compared to polymer electrolyte systems (tLi+ < 0.4) because of their potential to reduce the buildup of ion concentration gradients and suppress growth of lithium dendrites. The current review covers the fundamentals of SICPEs, including anionic unit synthesis, polymer structure design, and film fabrication, along with simulation and experimental results in solid‐state lithium–metal battery applications. A perspective on current challenges, possible solutions, and potential research directions of SICPEs is also discussed to provide the research community with the critical technical aspects that may advance SICPEs as solid electrolytes in next‐generation energy storage systems.