To provide a protective layer thermal transfer film which can form a protective layer that is superior in the water based ink fixing property, solvent-resistant property and, in particular, water-resistant property and also has a superior peeling property.The present invention relates to: a protective layer thermal transfer film, comprising: a thermally transferable protective layer on or over at least one part of one surface of a substrate film, wherein the protective layer is formed on or over the substrate by laminating at least a peeling layer serving as an outermost surface layer after transfer; and the peeling layer containing at least polyvinyl pyrrolidone, and a printed article with the protective layer transferred onto an image on the printed article.