The invention discloses a preparation method of a waterproof and moisture-permeable raincoat, wherein the preparation method comprises the following operation steps: (1) mixing methyl methacrylate, isobutyl methacrylate, ethyl dimethacrylate, an initiator, 2,3,3-trifluoroacrylic acid, deionized water and an emulsifier evenly, heating, and carrying out heat preservation, to prepare a polymerized emulsion; (2) adding dysprosium chloride and lutetium chloride to water, continuing to add sodium naphthenate, mixing and stirring evenly, heating to 65-70 DEG C, and after 2-3 h of heat preservation treatment, obtaining rare earth naphthenate; and (3) mixing the polymerized emulsion, dimethyl polysiloxane, a polyoxyethylene castor oil condensate and rare earth naphthenate evenly, preparing a raincoat coating, and then coating the surface of the woven raincoat with the raincoat coating, and carrying out drying treatment, to obtain the finished product. The prepared raincoat has the advantages ofgood softness, easy folding, excellent water resistance and moisture permeability, excellent oxidation resistance and long service life.