In this paper, we describe the fabrication, simulation and characterization of dense arrays of freestanding silver capped polystyrene nanotubes, and demonstrate their suitability for surface enhanced Raman scattering (SERS) applications. Substrates are fabricated in a rapid, low-cost and scalable way by melt wetting of polystyrene (PS) in an anodized alumina (AAO) template, followed by silver evaporation. Scanning electron microscopy reveals that substrates are composed of a dense array of freestanding polystyrene nanotubes topped by silver nanocaps. SERS characterization of the substrates, employing a monolayer of 4-aminothiophenol (4-ABT) as a model molecule, exhibits an enhancement factor of ~1.6 × 10(6), in agreement with 3D finite difference time domain simulations. Contact angle measurements of the substrates revealed super-hydrophobic properties, allowing pre-concentration of target analyte into a small volume. These super-hydrophobic properties of the samples are taken advantage of for sensitive detection of the organic pollutant crystal violet, with detection down to ~400 ppt in a 2 µl aliquot demonstrated.