Silane-based electrolyte is a promising candidate for safer electrochemical energy storage devices because it is thermally and electrochemical stable, less flammable and environmental benign. In this paper, electrochemical properties of one of the silane-based electrolytes, tri(ethylene glycol)-substituted trimethylsilane (1NM3)–lithium bis(oxalate)borate (LiBOB) was studied using LiMn2O4 as cathode and MAG graphite as anode. When combined with LiBOB as lithium salt, the 1NM3–LiBOB electrolyte can provide solid electrolyte interface (SEI) formation due to the reductive decomposition of LiBOB at first charging cycle. Compared to the electrolyte used in the conventional lithium-ion batteries, 1NM3–LiBOB electrolyte showed compatible battery performance in LiMn2O4/MAG chemistry. The AC impedance measurement indicates that the activation energy (E a ) obtained from the charge transfer impedance for 1NM3–LiBOB was higher than that of the state-of-the-art electrolyte. Due to its low conductivity, the rate capability of 1NM3–LiBOB electrolyte needs to be improved.