Polymers with repeating phosphoester linkages in the backbone are biodegradable materials that emerge as a promising class of novel biomaterials, especially in the field of drug delivery systems. In contrast to aliphatic polyesters, the pentavalency of the phosphorus atom offers a large diversity of structures and as a consequence a wide range of properties for these materials. In this paper, it is focused on the synthesis of well-defined polyphosphoesters (PPEs) by organocatalyzed ring-opening polymerization, improving the functionalities by combination with click reactions, degradation of functional PPEs and their cytotoxicity, and inputs for applications in drug delivery.