The post-modification of polypentafluorostyrene via the selective substitution of the para- fluorine by amine-functionalized molecules represents a versatile method for the preparation of functional materials. This communication presents the extension of this synthetic approach towards metallosupramolecular materials. First, the incorporation of terpyridines as metallo-supramolecular binding motifs is demonstrated, which enables the formation of a supramolecular crosslinked gel upon the addition of Fe(II) ions. Second, the linkage of phosphorescent iridium(III) complexes is reported yielding a copolymer that combines the excellent photophysical properties of the iridium(III) complex and the good solubility and processability of the polymer