Abstract: A laminated rubber stopper comprising a head portion and a leg portion which is to be inserted in an opening of a vessel, wherein at least a leg portion is laminated with a film of a copolymer of tetrafluoroethylene, ethylene and at least one fluorine-containing vinyl monomer copolymerizable with tetrafluoroethylene and ethylene, a molar ratio of tetrafluoroethylene and ethylene being from 62:38 to 90:10 and the amount of the fluorine-containing vinyl monomer being from 0.1 to 10% by mole based on the total number of mole of tetrafluoroethylene and ethylene, which has improved fitting with an opening of a vessel and sealing properties and can be produced with low failure rate.