Amphiphilic block copolymers containing phosphine moieties in the main chain are employed as macromolecular ligands for gold (1). The sequential living anionic copolymerization of isoprene (1) and the phosphaalkene, MesP=CPh2 (Mes = 2,4,6-trimethylphenyl) affords the block copolymer [PI](404)-b-[MesP-CPh2](32) (1a). The incorporation of gold(I) moieties into this functional copolymer is accomplished by treating 1 with THT center dot AuCl (THT = tetrahydrothiophene) which affords [PI](404)-b-[MesP(AuCl)-CPh2](32) (2a). Remarkably, dissolution of gold-functionalized 2 in n-heptane, a block-selective solvent for isoprene, affords spherical micelles with gold(l)-rich cores. Micelles were examined by transmission electron microscopy (TEM) and dynamic light scattering (DLS). We also prepared two additional copolymers with longer phosphine blocks and shorter PI segments: [PI](222)-b-(MesP(AuCl)-CPh2](77) (2b) and [PI](164)-b-[MesP(AuCl)-CPh2)(85) (2c). When assembled in isoprene-selective solvents, 2b forms wormlike structures and 2c, with the longest phosphine block, forms fascinating micron sized intertwined wormlike structures. This represents a new method to control the shape and size of gold(I) nanostructures.