The invention provides synthetic leather, a preparation method and application thereof in protecting shoes. The synthetic leather comprises a base cloth and surface polyurethane which is compounded on the base cloth through polyurethane adhesive, wherein the surface polyurethane consists of compound materials, breathable and waterproof polyurethane resin, and the compound materials comprises the following components in parts by weight: 75 to 95 percent of porous montmorillonoid, and 5 to 25 parts of polyether-modified silicone oil. The synthetic leather can be used for preparing protecting shoes. The invention adopts a method for adding mixture of the porous montmorillonoid and the polyether-modified silicone oil into the breathable and waterproof polyurethane resin to prepare the synthetic leather by dry process overlaying, and detection results prove that: the moisture permeability amount greatly exceeds the standard requirement in EN345 or ISO20345, and can achieve the S2 or S1 standard of the European Union; the water vapor permeance and water vapor permeability coefficient are 2.3mg/(cm2h) and 22.5mg/cm<2> respectively; and the prepared protecting shoes are more comfortable for wearing.