Rapid manufacturing of medical devices during unforeseen pandemics is imperative. In striving for manufacturing efficiency, photopolymerization has emerged as a viable approach for diverse healthcare applications in recent decades. Photopolymerization‐based 3D printing offers significant potential with a range of biocompatible materials (e.g., poly(ethylene glycol), cellulose, etc.) while minimizing waste generation. However, prevalent commercial photoinitiators used in this process are synthetic and environmentally unfriendly. Therefore, the naturally occurring and derived photoinitiators have drawn tremendous research interest due to their bioactivities and inherent environmental safety. This review comprehensively outlines the medical applications implemented by these photoinitiators, highlighting their inherent photoinitiation abilities. Moreover, it delves into the impact of substituent effects on the photoinitiation abilities of naturally derived photoinitiators.