Pure surfactant liquids and their binary mixtures, owing to the amphiphilic nature of the molecules involved, can exhibit nano-segregation and peculiar transport properties. The idea inspiring this work is that the possibility of including in such media salts currently used for technological applications should lead to a synergy between the properties of the salt and those of the medium. So the dynamic features of Bis(2-ethylhexyl)amine (BEEA) and bis(2-ethylhexyl)phosphoric acid (HDEHP) liquid mixtures were investigated as a function of composition and temperature by 1H NMR spectroscopy and rheometry. Inclusion of LitiumTrifluoromethanesulfonate (LiT) has been investigated by IR spectroscopy, Pulsed Field Gradient NMR and conductimetry methods to highlight the solubilizing and confining properties of these mixtures as well as the Lithium conductivity. It was found that BEEA/HDEHP binary liquid mixtures show zero-threshold percolating self-assembly with a maximum in viscosity and a minimum in molecular diffusionat 1:1 composition. Dissolution of LiT in such system can occur via confinement in the locally self-assembled polar domains. Despite this confinement, Li+ conduction is scarcely dependent on the medium composition thanks the possibility of a field-induced hopping decoupled by the medium structural and dynamical features.