Lacking viable electrolytes is one of the fundamental obstacles preventing the realization of rechargeable aluminum batteries. To date, the only electrolytes which can enable allowing reversible Al deposition-stripping with excellent chemical and electrochemical stability are the chloroaluminate ionic liquids (ILs). However, these kind of ILs are extremely corrosive due to the high concentration of chloride. To demonstrate the importance of the cathode/electrolyte interfacial stability in emerging rechargeable aluminum (Al) batteries, chemical compatibility between vanadium(V) oxide (V₂O₅), a widely studied cathode material for Al batteries, and the most common chloroaluminate ionic liquid electrolyte are studied. The potential reactions between V₂O₅ and Lewis acidic species (Al₂Cl₇^-) and Lewis neutral species (AlCl₄^-), respectively, and the resulting electrochemical properties are investigated with electrochemical analysis, spectroscopic characterizations including Raman and nuclear magnetic resonance (NMR) spectroscopy, supported by computational studies using methods based on density functional theory (DFT). Our studies clearly demonstrate that V₂O₅ reacts to both Al₂Cl₇^- and AlCl₄^-, and the reaction mechanisms are proposed and validated. We also developed new organic electrolyte for Al deposition at room temperature based on AlCl₃/g-butyrolactone (GBL) mixture in benzene. It is found that the solubility of AlCl₃ in GBL can be significantly enhanced by adding benzene as diluent. Besides, the coordination structure between AlCl₃ and GBL would change when the molar ratio of AlCl₃/GBL increased above 1:1, which lead to the generation of active species for Al deposition.