A new ionic liquid (IL) based on a “neutral” ligand, 4-propylpyridine, is obtained via complexation with AlCl3. It is found that the asymmetric cleavage of AlCl3 generates AlCl2+ and AlCl4−, and the former is coordinated by 4-Pr-Py to produce the Al-containing cations ([AlCl2(4-Pr-Py)2]+). The AlCl3/4-propylpyridine IL with a molar ratio of 1.3/1 is highly fluidic with a viscosity of 42.8 mPa · s and an ionic conductivity of 5.0 × 10−4 S/cm at room temperature. In contrast to conventional ILs for electroplating aluminum in which the electrochemically active species are Al-containing anions (for example Al2Cl7−), this new IL has an Al-containing cation as the electroactive species, which is beneficial to electrodeposition of aluminum.