The invention relates to an inorganic-matter doped multi-layer fluoric ion-exchange film and a preparation method thereof, pertaining to the field of functional macromolecular composite materials. The film is in a multi-layer structure, composed of fluoric ion-exchange resin and inorganic substance. The ion-exchange film prepared by the method has sound water-retaining performance, relatively high mechanical performance, chemical and mechanical stability, and is capableof preventing the penetration of hydrogen and methanol effectively.