To provide a protective layer thermal transfer film which can form a protective layer that is superior in water-based ink fixing property, solvent-resistant property and, in particular, water-resistant property and also has a superior peeling property.A protective layer thermal transfer film, comprising:at least a release layer, anda protective layer, formed on one surface of a substrate film;the release layer being formed from at least a silicone-modified resin and silicone oil; anda printed article with the protective layer transferred onto an image on the printed article.