In this paper, PEDOT/PSS-ZnO coaxial nanocables with diverse inner core sizes are prepared by a new and facile method that involves two-steps: the synthesis of ZnO nanoparticles through a sol-gel process, followed by dewetting-control led self-assembly of the nanoparticles and charged polymers to generate a cable-like nanostructure with the aid of a vacuum. The nanocables have an outer diameter of ca. 100 nm with a polycrystalline ZnO inner core of 7-25 nm in diameter. The length and morphology of the nanocables are determined by external vacuum conditions as well as the ZnO concentration in the composite. A photoluminescence study shows an enhanced green light emission arising from ZnO with a size-dependence feature.