Tris(methoxy polyethylenglycol) borate ester (B-PEG) and aluminum tris(polyethylenglycoxide) (Al-PEG) were used as electrolyte solvent for lithium ion battery, and the electrochemical property of these electrolytes were investigated. These electrolytes, especially B-PEG, showed poor electrochemical stability, leading to insufficient discharge capacity and rapid degradation with cycling. These observations would be ascribed to the decomposition of electrolyte, causing formation of unstable passive layer on the surface of electrode in lithium ion battery at high voltage. However, significant improvement was observed by the addition of aluminum phosphate (AlPO4) powder into electrolyte solvent. AC impedance technique revealed that the increase of interfacial resistance of electrode/electrolyte during cycling was suppressed by adding AlPO4, and this suppression could enhance the cell capabilities. We infer that dissolved AlPO4 components formed electrochemically stable layer on the surface of electrode.