Molecular photoswitches can undergo isomerization under light exposure, making them uniquely attractive for high spatiotemporal resolution remote control of biological functions. Visible and near‐infrared (NIR) light, with their low energy consumption, high safety, and strong tissue penetration, are particularly suitable for biological applications. Therefore, developing visible‐ and NIR light‐driven molecular photoswitches for biological use is of great significance. This review introduces the most common visible‐ and NIR light‐driven molecular photoswitches and presents the state‐of‐art of their applications in bioimaging, biosensing, drug delivery, photocontrolled cancer phototherapy, and photopharmacology. The opportunities and challenges of the photoswitches for their future development in biological applications are outlined.