Abstract: The electrodeposition of aluminum in ionic liquid has broad application prospects, and additives are an effective way to improve the performance of the aluminum coating. However, the relevant mechanism behind this remains to be clarified. In the present work, the effects of dichloromethane (DCM) and toluene (C₇H₈) on the microstructure, physicochemical properties, and aluminum electrodeposition with 1-butyl-3-methylimidazolium chloride/aluminum chloride (BMIMCl/AlCl₃) were studied using quantum chemistry and molecular dynamics simulation. It is found that DCM easily forms hydrogen bonds with anions and cations of ionic liquids. Since DCM is distributed between anion and cation, the distance between the anion and cation increases, and the interaction energy decreases. As a result, the diffusion ability of anions and cations is enhanced, and the aluminum complex anions tend to exist in the form of \rmA\rml_2\rmCl_7^ - . The viscosity of the system decreases, and the conductivity increases, so the electrochemical properties of the system are significantly improved, which are in good agreement with the experimental values. C₇H₈ is adsorbed on the protruding part of the electrode surface in a flat way, which plays a leveling role and results in a flat white coating. Alternatively, DCM easily interacts with the electroactive ion \rmA\rml_2\rmCl_7^ - , which makes it difficult to reduce this electroactive ion. At the same time, the concentration of the electroactive ion decreases as the concentration of the additive is increased, which leads to a large overpotential in the electrochemical process, resulting in a decrease in the electrode reaction rate that plays a role in grain refinement. Moreover, the interaction between DCM and cations is also strong, and they can be adsorbed on the protruding part of the electrode surface during the electrochemical process, playing a certain leveling role. Therefore, the addition of DCM can obtain specular gloss deposits. The effect of C₇H₈ on the interaction between anions and cations is not as good as DCM, which consequently results in inferior electrochemical properties compared to DCM. Therefore, DCM is more favorable for the electrodeposition of aluminum than the aromatic hydrocarbon C₇H_8.