Significance Green coloration of vertebrates is normally attributed to pigments and structural components inside skin chromatophores cells. However, these components do not account for the vivid blue-green colors of hundreds of species of frogs with sparse chromatophores. Our study shows that green coloration originates in proteins of the serpin superfamily that bind the pigment biliverdin, modulating its absorbance properties. Using a South American treefrog, we demonstrated that these serpins have a clear ecological role in modulating the reflectance properties and rendering animals cryptic in the foliage even in the near-infrared portion of the spectrum. These findings open up exciting research perspectives both in biochemistry and evolution of serpins, as well as in the study of extracellular protein-mediated coloration in vertebrates.