Thermotropic nematic electrolytes are obtained by dissolving lithium salts within nematogens bearing poly(ethylene oxide) (PEO) chains located either at the termini or in the middle of the rigid nematogen cores (see Figure). The ionic conductivity is enhanced for alkali salt/liquid crystal mixtures with short terminal PEO chains. Self-diffusion coefficients of the mobile species and the fluorine-fluorine dipolar couplings are determined by NMR, and provide insight into the ionic conductivity mechanism.