Deoxyribonucleic acid is probably the most prominent polyphosphoester (PPE). In materials science, polymers based on esters and amides of phosphoric acid are interesting materials for various applications, ranging from flame-retardant additives to polymers for biomedical applications. This short communication summarises the features of selective degradability in PPEs and polyphosphoramidates, depending on the binding pattern around the central phosphorus. In addition, polyphosphonates carrying stable P–C bonds and main-chain polyphosphorodiamidates show distinctively different hydrolysis kinetics. The applications of such materials may depend on the eventual degradability, but different timescales and different conditions need to be considered. This article summarises recent developments of the field and discusses related applications.