In this work, TiO2-based ionogel electrolytes (TIEs), TiO2/ionic liquid/LiTFSI, are prepared by a one-pot sol–gel processing. The electrochemical performance and potential application in lithium metal batteries (LMBs) of TIEs are evaluated for the first time. It is found that the as-prepared TIE system reveals liquid-like high ionic conductivity, good electrochemical stability and ability to promote uniform lithium electrodeposition. Specifically, LMBs containing the TIE show high discharge capacity and good capacity retention at 25 °C under the 0.1C rate. Also, acceptable rate performance and low-temperature discharge ability can be obtained.