Ca metal anode rechargeable batteries are seen as a sustainable high-energy density and high-voltage alternative to the current Li-ion battery technology due to the low redox potential of Ca metal and abundance of Ca. Electrolytes are key enablers on the path towards next-generation battery systems. Within this work, we synthesize a new calcium tetrakis(hexafluoroisopropyloxy) aluminate salt, Ca[Al(hfip)4]2, and benchmark itversusthe state-of-the-art boron analogue Ca[B(hfip)4]2. The newly developed aluminate-based electrolyte exhibits improved performance in terms of conductivity, Ca plating/stripping efficiency, and oxidative stability as well as Ca battery cell performance. A marked improvement of 0.5 V higher oxidative stability can pave the path towards high-voltage Ca batteries. A critical issue of solvent quality during salt synthesis is identified as well as solvent decomposition at the Ca metal/electrolyte interface, which leads to passivation of the Ca metal anode. However, the new aluminate salt with preferable electrochemical properties over the existing boron analogue opens up a new area for future Ca battery research based on aluminium compounds.