Single-ion conductors have garnered attention in energy storage systems as a promising alternative to currently widespread electrolytes that allow migration of cations and anions. However, ion transport phenomena of most single-ion conductors are affected by strong ion (e.g., Li+)-ion (immobilized anionic domains) interactions and tortuous paths, which pose an obstacle to achieving performance breakthroughs. Here, we present a Li+-centered G-quadruplex (LiGQ) as a class of single-ion conductor based on directional Li+ slippage at the microscopic level. A guanine derivative with liquid crystalline moieties is self-assembled to form a hexagonal ordered columnar structure in the LiGQ, thereby yielding one-dimensional central channels that provide weak ion-dipole interaction and straightforward ionic pathways. The LiGQ exhibits weak Li+ binding energy and low activation energy for ion conduction, verifying its viability as a new electrolyte design.