Brightly phosphorescent gold-based metallopolymers have been synthesized by reaction of nonluminescent reactants comprised of the commercially available polymer PVP = poly (4-vinylpyridine) and the Au(1) precursors [Au(C6X5)THT] (X = F or Cl; THT = tetrahydrothiophene). The metallopolymer products exhibit remarkable photoluminescence properties including high solid-state quantum yield (up to 0.63 at RT) and coarse- and fine-tuning to multiple phosphorescence bands across the visible spectrum via luminescence thermochromism and site-selective excitation. The emissions are caused by intrachain and interchain aurophilic interactions between the linear Au(I) complexes in the metallopolymers. This investigation provides further manifestations of interesting chemistry and photophysics in N-heterocyctic coordination compounds of Au(I) by expansion from the small-motecule to the metallopolymer regime. The spectroscopic and material properties of the new class of metallopolymers are desirable for future studies that will utilize them as emitters for photonic applications such as polymer tight-emitting diodes and sensors.