Abstract All‐solid‐state batteries (ASSBs) are widely regarded as one of the most promising candidates for next‐generation energy storage technologies. Among the various components of ASSBs, solid polymer electrolytes (SPEs) have attracted significant attention due to their excellent mechanical toughness, low densities, ease of processing, and good interfacial contact with electrodes. In recent years, liquid crystal polymer (LCP) electrolytes have emerged as a research hotspot. Unlike traditional classifications of dielectric and non‐dielectric phases, the unique ordered self‐assembled structures of LCP electrolytes can provide highly efficient ion transport pathways. This perspective presents a systematic perspective on regulating the performance of lithium‐ion batteries (LIBs) (especially ASSBs) through the synergistic combination of dielectric and liquid crystal (LC) phases. The aim of this work is to offer detailed and timely insight into the advantages and disadvantages of polymers and their composite electrolytes from the perspectives of dielectric and ferroelectric phases, while also evaluating the potential of LCPs from the viewpoints of LC and non‐LC phases. By combining the advantages of dielectric and LC phases, this work envisions a future for SPEs where ferroelectric LCPs and their composites emerge as a new class of SPEs.