Herein, we describe the synthesis of bench-stable organometallic Au(III) terminated polymer reagents. These reagents mediate the chemoselective S-arylation of thiol-containing small molecules and polymers to yield functionalized mono-telechelic polymers and diblock copolymers, respectively. These transformations proceed rapidly within minutes and produce conjugates in quantitative conversion, making this strategy a robust addition to the polymer functionalization toolbox.