- Development of technologies for constructing three-dimensional (i.e. non-planar) transparent conductive electrodes from polymeric materials is a major goal in diverse applications, including optoelectronic devices, flexible electronics, photovoltaics, and others. We present a facile new strategy for creating conductive, transparent gold layering on polystyrene, a widely-used polymer, in different shapes and surface morphologies. The approach is based upon amine functionalization of the polystyrene surface followed by incubation in an aqueous solution of Au(SCN)4− and brief plasma treatment. We show that this simple deposition process resulted in a homogeneous, transparent, and highly conductive crystalline Au coating. Importantly, electrical conductivity was attained for long distances, even in highly non-planar surfaces containing physical barriers. We further show that the approach can be employed for fabrication of conductive hollow tubes using electrospun polystyrene fibers as templates. The new synthesis scheme might make possible varied applications in polymer-based electronic and photonic devices.