Structural blue colors are common in animals, with the tissue nanostructures and material systems that produce them—especially bright blues—typically based on highly ordered nano‐architectures. In this study, we describe an unusually bright and angle‐independent structural blue from the skin of ribbontail stingray, arising from a more disordered array of scattering elements with a previously undescribed core–shell ultrastructure, involving nano‐vesicles enclosing guanine nano‐platelets. We show that this skin architecture functions as an intracellular photonic glass, coherently scattering blue, while broadband absorption from closely associated melanophores obviates the low color saturation typical for photonic glasses. Our characterization of skin ultrastructure and color in a stingray demonstrates how disordered systems can be harnessed to produce brilliant hues while illustrating that the capacity for guanine‐based colors likely arose extremely early in vertebrate evolution. Moreover, the material‐structure‐function associations underlying ribbontail stingray coloration, employing two distinct photonic phenomena, illustrate how the evolution of nanoscale architectures can have profound effects at much larger size scales (e.g., in visual ecology and communication), and provide fundamental guidelines for color‐saturated manmade photonic glasses.