The ever-increasing demand for high-performance batteries has inspired the relentless pursuit of advanced electrolytes with well-defined ordered structure as a key-enabling material. However, most battery electrolytes reported to date have shown randomly distributed and reticulated ion channels due to lack of attention to structure ordering. As a molecular structure design to address this issue, we present a class of self-assembled polymer Li-ion conductors. A covalent organic framework (COF)-based ion conductor featuring the vertically stacked 2D repeating units enables directional and solvent-free ion transport. 3DOM-structured separator membranes (fabricated via self-assembly of nanoparticles) and Li protective layers based on cholesteric liquid crystalline-structured nanocellulose arrays provide facile and uniform ion fluxes, which are difficult to achieve with conventional polymer materials used in batteries.