Abstract Photopharmacology harnesses photoswitchable molecules to reversibly and precisely modulate biological activities, offering exceptional spatial and temporal control through non‐invasive illumination. Traditionally, azobenzene‐based photoswitches have dominated this field due to their robust photochemistry and synthetic simplicity. Recent advances, however, have introduced diverse alternatives featuring novel photoresponsive cores beyond the classical azo (–N=N–) moiety. These novel molecular scaffolds exhibit gratifying features, including exceptional thermal bistability, near‐quantitative photoconversion efficiencies, and long‐wavelength photoactivation, significantly improving their suitability for biological applications. This review systematically highlights recent progress in photopharmacology beyond azobenzenes, critically discusses their pros and cons, and provides valuable insights for the rational selection of photoswitches tailored to specific therapeutic contexts, ultimately aiming to broaden their biomedical applicability and facilitate advanced precision medicine.