Based on the voltammetric behaviour of a series of methyl-substituted benzenes in 1M LiPF6/EC-DMC electrolyte, xylene was selected and tested as an electrolyte additive for overcharge protection of Li-ion batteries. From the overcharge curves, CV behaviour and SEM observations of the cells in the presence of xylene, it was found that the additive can polymerize at the overcharged voltage to form a dense layer of isolating polymer film at the cathode surface, which blocks off further oxidation of the electroactive material and electrolyte and, therefore, improves the overcharge tolerance of the Li-ion battery. In addition, the xylene additive has shown only a slight influence on the cycling behaviour.