摘要： In this work, a joint experimental and computational study on the synthesis, self-assembly, and ionic conduction characteristics of a new conjugated liquid crystal quaterthiophene/poly(ethylene oxide) (PEO4) consisting of terminal tetraethyleneglycol monomethyl ether groups on both ends of a quaterthiophene core is performed. In agreement with molecular dynamic simulations, temperature-dependent grazing-incidence wide angle X-ray scattering and X-ray diffraction indicate that the molecule spontaneously forms a smectic phase at ambient temperature as characterized both in bulk and thin film configurations. Significantly, this smectic phase is maintained upon blending with bis(trifluoro-methanesulfonyl)imide as ion source at a concentration ratio up to r = [Li+]/[EO] = 0.05. Nanosegregation between oligothiophene and PEO moieties and π–π stacking of thiophene rings lead to the formation of efficient 2D pathways for ion transport, resulting in thin-film in-plane ionic conductivity as high as 5.2 × 10?4 S cm?1 at 70 °C and r = 0.05 as measured by electrochemical impedance spectroscopy. Upon heating the samples above a transition temperature around 95 °C, an isotropic phase forms associated with a pronounced drop in ionic conductivity. Upon cooling, partial and local reordering of the conducting smectic domains leads to an ionic conductivity decrease compared to the as-cast state.