Recent insights into the function and composition of cell membranes have transformed our understanding from primarily viewing these structures as passive barriers to recognizing them as dynamic entities actively involved in many cellular functions. This review highlights advances in the photopharmacology of phospholipids, emphasizing in particular the role of diacylglycerophospholipids and the impact of their polymorphic nature on synthetic and cellular membrane properties and metabolic processes. We explore photoswitchable diacylglycerophospholipids, termed 'photolipids', which permit precise, reversible modifications of membrane properties via light-induced isomerization. The ability to optically switch phospholipid properties has potential applications in controlling membrane dynamics, protein function, and cellular signaling pathways, and offers promising strategies for drug delivery and treatment of diseases. Developments in azobenzene and hemithioindigo based photolipids are discussed, underscoring their utility in biomedical and biomaterial science applications due to their unique photophysical properties.