Rechargeable calcium (Ca) batteries have the prospect of highenergy and low-cost. However, the development of Ca batteries is hindered due to the lack of efficient electrolytes. Herein, we report novel calcium tetrakis(hexafluoroisopropyloxy)borate Ca[B(hfip)₄]₂ based electrolytes exhibiting reversible Ca deposition at room temperature, a high oxidative stability up to 4.5 V and high ionic conductivity >8 mS cm¯¹. This finding opens a new approach towards room-temperature rechargeable calcium batteries.