Modern
electrochemical and electronic devices require advanced
electrolytes. Liquid crystals have emerged as promising electrolyte
candidates due to their good fluidity and long-range order. However,
the mesophase of liquid crystals is variable upon heating, which limits
their applications as high-temperature electrolytes, e.g., implementing
anhydrous proton conduction above 100 °C. Here, we report a highly
stable thermotropic liquid-crystalline electrolyte based on the electrostatic
self-assembly of polyoxometalate (POM) clusters and zwitterionic polymer
ligands. These electrolytes can form a well-ordered mesophase with
sub-10 nm POM-based columnar domains, attributed to the dynamic rearrangement
of polymer ligands on POM surfaces. Notably, POMs can serve as both
electrostatic cross-linkers and high proton conductors, which enable
the columnar domains to be high-temperature-stable channels for anhydrous
proton conduction. These nanochannels can maintain constant columnar
structures in a wide temperature range from 90 to 160 °C. This
work demonstrates the unique role of POMs in developing high-performance
liquid-crystalline electrolytes, which can provide a new route to
design advanced ion transport systems for energy and electronic applications.