Methods of blocking stains on a substrate to be painted are disclosed, as are stain-blocking composites that are useful according to the disclosed methods. In a broad aspect, the methods include the steps of contacting a stained portion of the substrate with a dry film layer; applying pressure to the dry film layer to cause the dry film layer to adhere to the stained portion of the substrate and to at least a portion of the substrate adjacent the stained portion of the substrate; and subsequently coating the dry film layer and the adjacent substrate with one or more additional liquid coating layers. Stain blocking composites useful according to the methods described include a release layer, to which the pressure is applied; a dry film layer, that can be clear or pigmented, that serves to block the stain; and an optional adhesive layer, intended to assist in adhering the dry film layer to the stained portion of the substrate and to at least that portion of the substrate adjacent the stained portion of the substrate.