The promise of polyhydroxamic acid ligands for the selective chelation of the f‐block elements is becoming increasingly more apparent. The initial studies of polyhydroxamic acid siderophores showed the formation of highly stable complexes with Pu^IV, but a higher preference for Fe^III hindered effective applications. The development of synthetic routes toward highly pure and customizable ligands containing multiple hydroxamic acids allowed for the growth of new classes of compounds. Although the first round of these ligands focused on the incorporation of siderophore‐like frameworks, the new synthetic strategies led to small molecules of various frameworks and even resins for applications in the field of f‐block element separations and biological desorption. Unfortunately, a lack of consistent stability‐constant data makes direct comparisons across this body of work difficult. More studies into the stability constants and separations of the f‐block elements in a variety of pH ranges is necessary to truly realize the potential for polyhydroxamic acid ligands.