Morphology, dimension, size, and surface chemistry of gold nanoparticles are critically important in determining their optical, catalytic, and photothermal properties. Although many techniques have been developed to synthesize various gold nanostructures, complicated and multistep procedures are required to generate three-dimensional, dendritic gold nanostructures. Here, we present a simple method to synthesize highly branched gold nanodendrites through the well-controlled reduction of gold ions complexed with a catechol-grafted polymer. Dextran grafted with catechols guides the morphological evolution as a polymeric ligand to generate dendritic gold structures through the interconnection of the spherical gold nanoparticles. The reduction kinetics, which is critical for morphological changes, is controllable using dimethylacetamide, which can decrease the metal–ligand dissociation and gold ion diffusivity. This study suggests that mussel-inspired polymer chemistry provides a simple one-pot synthetic route to colloidal gold nanodendrites that are potentially applicable to biosensing and catalysis.