In this work, we evaluated the chemical compatibility of 1.0m (molality) lithium bis(oxalate)borate (LiBOB) 1:1 (w/w) propylene carbonate (PC)/ethylene carbonate (EC) liquid electrolyte with lithium metal and spinel LiMn2O4 cathode using storage and cycling tests at high temperatures. Impedance analyses show that LiBOB and lithium are very compatible due to the formation of a stable passivation layer on the surface of lithium. Cycling tests of Li/Cu and Li/LiMn2O4 cells, respectively, show that lithium can be plated and stripped in LiBOB-based electrolyte with more than 80% cycling efficiency, and that this electrolyte can support LiMn2O4 cycling reversibly up to 60°C without visible capacity loss. Using LiBOB-based liquid electrolyte and porous Kynar® membrane, microporous gel electrolyte (MGE) Li-ion cells were assembled and evaluated. Results show that the MGE cell presents an improved cycling performance compared with a liquid cell, especially at elevated temperatures. It is confirmed that the LiBOB-based gel electrolyte Li-ion batteries can be operated at 60°C with good capacity retention.