Photoswitches are important molecular tools to precisely control the behavior of matter by using light irradiation. They have found application in virtually all applied chemical fields from chemical biology to material sciences. However, great challenges remain in advanced property design including tailored chiroptical responses or water solubility. Here, hemiphosphoindigo (HPI) photoswitches are presented as capable phosphorus-based photoswitches and a distinct addition to the established indigoid chromophore family. Phosphinate is embedded in the core indigoid chromophore and the resulting optimized photoswitches display high thermal stabilities, excellent fatigue resistance and high isomer enrichment. A series of planar, twisted and heterocyclic HPIs are investigated to probe design strategies for advantageous photophysical properties. The phosphinate provides a platform for easily accessible, water-soluble photoswitches, especially interesting for biological applications. Its chiral nature further allows light-induced modulation of chiroptical properties. HPIs therefore open up a distinct structural space for photoswitch generation and advanced light-responsive applications.