A potential-sensitive separator is prepared by incorporating an electroactive poly (4-methoxytriphenylamine) (PMOTPA) into the micropores of a commercial porous polyolefin film and tested as an internal voltage control device for overcharge protection of LiFePO4/Li4Ti5O12 lithium ion batteries. The experimental results demonstrate that the PMOTPA polymer embedded in the separator can be electrochemically p-doped at overcharged voltages into an electrically conductive state, producing an internal conducting bypass for shunting the charge current to maintain the charge voltage of LiFePO4/Li4Ti5O12 cells at a safety value less than 2.6V, thus protecting the cell from voltage runaway. Since this type of the separators works reversibly and has no any discernable impact on the battery performances, it may offer a self-protection mechanism for development of safer lithium ion batteries.