Photoremovable protecting groups (PPGs) offer a straightforward solution for the temporary inactivation of biologically active substrates and their subsequent controlled release by light irradiation. Their relatively easy design and mode of application have made them useful tools for studying dynamic biological processes in vitro and in vivo. Recently, there has been a growing body of data investigating their potential application in the development of drug delivery systems. Of the various PPG scaffolds in use, quinoline photocages have a history of about 20 years. The structure‐property relationships of quinoline PPGs, as well as alternative multibranch designs based on quinoline monomers have been thoroughly studied both experimentally and theoretically. Therefore, quinoline PPGs serve as a representative study of PPG development, showing how the various applications of quinoline photocages followed the chemical optimization or how the applications drove the chemical design. Since the raison d’être of PPGs lies in their application for light‐activated release of various substrates or performing light‐activated structural changes in materials, it is crucial to understand how PPGs are selected and utilized by their end‐users, who are often not chemists themselves. Therefore, we discuss whether the conclusions drawn from the selected quinoline PPG family could lead to more general insights for the field as whole. As PPG‐related applications still rely heavily on a limited number of chemical scaffolds, it is worth considering, what could be the reasons for the slow uptake of novel chemical scaffolds.