Ion interactions in a neutral ambient-temperature tetrachloroaluminate melt were studied using FTIR and NMR techniques at different lithium concentrations. The effect of lithium on the imidazolium cation is shown to be very small, but it strongly affects the AlCl4- anion, leading to the perturbation of the T-d symmetry and the appearance of extra absorption peaks due to lithium interactions. The interactions are strong in the LiCl-ImCl-AlCl3 melt, and the absorbances of the related vibration peaks are linearly dependent on the lithium concentration. Under high Li+ concentrations, an obvious change in the conductivity, density, viscosity, and Li-7 NMR shifts is observed when the mole ratio of AlCl4-:Li+ is less than 3.5:1 to 5:1, depending on different measuring techniques. A model with the formation of a network-like structure of Li+/AlCl4- under high Li+ concentrations was proposed to explain the above changes.