Block copolymer self-assembly has proven to be an effective route for the fabrication of photonic films and, more recently, photonic pigments. However, despite extensive research on this topic over the past two decades, the palette of monomers and polymers employed to produce such structurally colored materials has remained surprisingly limited. In this perspective, we summarize the commonly used block copolymer systems in the literature (considering both linear and brush architectures) and rationalize their use from the point of view of both their historical development and physicochemical constraints. Finally, the current challenges facing the field are discussed and promising new areas of research are highlighted to inspire the community to pursue new directions.